CN118598526A - Glass-ceramics, glass-ceramics products and methods for producing the same - Google Patents

Abstract

The invention provides a glass ceramic and a glass ceramic product with excellent mechanical property and optical property. The microcrystalline glass product contains ：SiO₂：65～75％;Al₂O₃：1～8％;Li₂O：14～25％;P₂O₅+ZrO₂：0.5～6％. by mole percent, has excellent mechanical property and optical property through reasonable component design, and is suitable for electronic equipment or display equipment.

Description

Glass-ceramics, glass-ceramics products and methods for producing the same

This application is a divisional application for the invention patent application with application number 202110901872.5, application date August 6, 2021, and name “Microcrystalline glass, microcrystalline glass products and manufacturing methods thereof”.

Technical Field

The present invention relates to a glass-ceramic, and in particular to a glass-ceramic and a glass-ceramic product having excellent mechanical and optical properties and a method for manufacturing the same.

Background Art

In recent years, cover glass is used to protect the display or as a back cover in portable electronic devices such as smartphones and PADs. In addition, protective objects are also used to protect lenses on automotive optical equipment, monitoring and security equipment, etc. These materials used as cover glass or protective objects are required to have high visible light transmittance and excellent color balance, that is, the relevant cover glass is required to have excellent optical properties. On the other hand, portable electronic devices will inevitably fall or drop during use, which requires the cover glass to have excellent mechanical properties (such as drop resistance, etc.) to minimize the probability of electronic devices being broken due to falling or dropping. In the prior art, chemically strengthened glass is often used as a material for the above-mentioned cover glass. However, the previous chemically strengthened glass is easy to crack vertically from the glass surface, so when the portable electronic device falls, the probability of breaking will increase.

Glass-ceramics can have physical properties that cannot be obtained in chemically strengthened glass by forming dispersed crystals inside, and because of the formation of microcrystals in the glass, its bending resistance and wear resistance have obvious advantages over general glass. Based on the above advantages, there is a trend to apply glass-ceramics or processed glass-ceramics products to display devices or electronic devices with high requirements for drop resistance, pressure resistance, and scratch resistance. However, glass-ceramics in the prior art have defects such as high haze value and low drop resistance, which makes it difficult to meet the application requirements of display devices or electronic devices with high requirements.

Summary of the invention

The technical problem to be solved by the present invention is to provide a microcrystalline glass and microcrystalline glass products with excellent mechanical properties and optical properties.

The technical solution adopted by the present invention to solve the technical problem is:

(1) A glass-ceramic product, wherein the components thereof are expressed in molar percentages as follows: SiO ₂ : 65-75%; Al ₂ O ₃ : 1-8%; Li ₂ O: 14-27%; and P ₂ O ₅ +ZrO ₂ : 0.5-6%.

(2) The glass-ceramic product according to (1), further comprising, expressed in molar percentage, ZnO+MgO: 0-4%; and/or _Na2O : 0-3.5%; and _/ or _B2O3 : 0-3%; and/or _K2O : 0-3%; and/or SrO: 0-3%; and/or BaO: 0-3%; and/or CaO: 0-3%; and/or _TiO2 : 0-3%; and/or _{Y2O3 :} 0-3%; and/or a clarifier: 0-1%.

(3) Microcrystalline glass products, whose components are expressed in molar percentage, consisting of _SiO2 : _65-75 %; _Al2O3 : 1-8%; _Li2O : _14-27 %; _P2O5 +ZrO2 _: 0.5-6% _; ZnO+MgO _: 0-4%; Na2O: 0-3.5%; B2O3: 0-3%; _K2O : _0-3 %; SrO: 0-3%; _BaO : 0-3%; CaO: 0-3%; _TiO2 : 0-3%; _Y2O3 : 0-3%; and clarifier: 0-1%.

(4) Glass-ceramic products, whose components, expressed in weight percentage, contain: SiO ₂ : 65-75%, Al ₂ O ₃ : 1-8%, Li ₂ O: 14-27%, and the crystal phase of the glass-ceramic products contains lithium silicate, and/or quartz and quartz solid solution, and/or petalite.

(5) A glass-ceramic product comprising SiO ₂ , Al ₂ O ₃ and Li ₂ O as essential components, wherein the crystal phase of the glass-ceramic product comprises lithium silicate, and the drop resistance of the glass-ceramic product is above 1700 mm.

(6) The glass-ceramic product according to any one of (4) or (5), wherein the components, expressed in molar percentage, are: _SiO2 : 65-75%; _Al2O3 : _1-8 %; Li2O: 14-27%; _{P2O5 +} ZrO2: 0.5-6%; ZnO+MgO: 0-4%; _Na2O : 0-3.5%; B2O3 _: 0-3%; K2O: _0-3 %; SrO: 0-3%; BaO: 0-3%; CaO _: 0-3%; _TiO2 : _0-3 %; _{Y2O3 :} 0-3%; _and a clarifier: 0-1%.

(7) The glass-ceramic product according to any one of (1) to (6), wherein the composition is expressed in molar percentage, wherein: (Li ₂ O + ZrO ₂ ) / (ZnO + MgO) is 10 or more, preferably (Li ₂ O + ZrO ₂ ) / (ZnO + MgO) is 12 to 45, more preferably (Li ₂ O + ZrO ₂ ) / (ZnO + MgO) is 13 to 40, and further preferably (Li ₂ O + ZrO ₂ ) / (ZnO + MgO) is 15 to 35.

₍ 8) The glass-ceramic product according to any one of (1) to (6 ₎ , wherein the composition is expressed in molar percentage, wherein: ( _B2O3 + _Na2O + _ZrO2 )/( _Al2O3 +MgO) is 0.05 to _1.5 , preferably ( _{B2O3 + Na2O} + _ZrO2 )/( _Al2O3 +MgO) is 0.1 to 1, _more preferably ( _B2O3 + _{Na2O +ZrO2)/(Al2O3+MgO) is 0.15 to 0.8, and further preferably (B2O3 + Na2O + ZrO2 )} /( _Al2O3 +MgO) is _0.2 to 0.7 _.

(9) The glass-ceramic product according to any one of ( ₁ ) to (6), wherein the composition is expressed in molar percentage, wherein: ( _SiO2 + _Li2O )/( _Al2O3 + ZnO+MgO) is 5 to 40, preferably ( _SiO2 + _Li2O )/( _Al2O3 + ZnO+MgO) is 8 to 30, more preferably ( _SiO2 + _Li2O )/( _Al2O3 + ZnO+MgO ₎ is ₁₀ to 25, and further preferably ( _SiO2 + _Li2O )/( _Al2O3 + ZnO+MgO) is 11 _to 20.

(10) The glass-ceramic product _according to any one of (1) to ( ₆ ), wherein the composition is expressed in molar percentage, wherein: ( _SiO2 + _Al2O3 + _Li2O + _Na2O + _ZrO2 ) / ( _P2O5 + MgO) is ₃₀ to 90, preferably ( _SiO2 + _Al2O3 + _Li2O + _Na2O + ZrO2) / ( _P2O5 + MgO) is 35 to 80, more preferably ( _SiO2 + _Al2O3 + _Li2O + _Na2O + _ZrO2 ) / ( _P2O5 + MgO) is ₃₈ to 75, _and further preferably ( _SiO2 + _Al2O3 + _Li2O + _Na2O + _ZrO2 ) / ( _P2O5 + MgO) is _{40 to 70 .}

(11) The glass-ceramic product according to any one of (1) to (6), wherein the composition is expressed in molar percentage, wherein: (SiO ₂ +Al ₂ O ₃ )/(P ₂ O ₅ +ZrO ₂ ) is 12 to 75, preferably (SiO ₂ +Al ₂ O ₃ )/(P ₂ O ₅ +ZrO ₂ ) is 15 to 70, more preferably (SiO ₂ +Al ₂ O ₃ )/(P ₂ O ₅ +ZrO ₂ ) is 17 to 65, and further preferably (SiO ₂ +Al ₂ O ₃ )/(P ₂ O ₅ +ZrO ₂ ) is 20 to 60.

(12) The glass-ceramic product according to any one of (1) to (6), wherein the components are expressed in molar percentages, wherein: _SiO2 : 67-73%, preferably _SiO2 : 68-72%; and/or _{Al2O3 :} 2-6.5%, preferably _Al2O3 : _3-6 %; and/or _Li2O : 15.5-25%, preferably _Li2O : 17-23.5%; and/or ZnO+MgO: 0.1-4%, preferably ZnO+MgO: 0.2-3%, more preferably ZnO+MgO: 0.5-2%; and/or _P2O5 +ZrO2: 1-4%, preferably _P2O5 +ZrO2: _1.2-3 %; and/or _Na2O : 0.5-3%, preferably _Na2O : 0.5-2.5%; and/or _B2O3 : 0.1-4%, preferably ZnO ₊ MgO: 0.2-3% _, more preferably ZnO ₊ MgO: _0.5-2 %; : 0.5-2.5%, preferably B ₂ O ₃ : 0.5-2%; and/or K ₂ O: 0-2%, preferably K ₂ O: 0-1.5%; and/or SrO: 0-2%, preferably SrO: 0-1%; and/or BaO: 0-2%, preferably BaO: 0-1%; and/or CaO: 0-2%, preferably CaO: 0-1%; and/or TiO ₂ : 0-2%, preferably TiO ₂ : 0-1%; and/or Y ₂ O ₃ : 0-2%, preferably Y ₂ O ₃ : 0-1%; and/or clarifier: 0-0.5%, preferably clarifier: 0-0.2%.

(13) The glass-ceramic product according to any one of (1) to (6), wherein the components are expressed in molar percentage, wherein: ZnO: 0-2%, preferably ZnO: 0-1.5%, more preferably ZnO: 0-1%; and/or MgO: 0-4%, preferably MgO: 0-3%, more preferably MgO: 0-1.5%; and/or P ₂ O ₅ : 0-3%, preferably P ₂ O ₅ : 0.2-2%, more preferably P ₂ O ₅ : 0.4-1.5%, further preferably P ₂ O ₅ : 0.5-1%; and/or ZrO ₂ : 0-4%, preferably ZrO ₂ : 0.2-3.5%, more preferably ZrO ₂ : 0.5-3%, further preferably ZrO ₂ : 0.7-2.5%.

(14) According to any one of the microcrystalline glass products described in (1) to (6), the crystalline phase in the microcrystalline glass product contains lithium silicate; and/or quartz and quartz solid solution; and/or petalite. Preferably, the crystalline phase in the microcrystalline glass product contains lithium disilicate and petalite, and the total content of lithium disilicate and petalite has a higher weight percentage than other crystalline phases. More preferably, the total content of lithium disilicate and petalite crystalline phases accounts for 50-80% of the weight percentage of the microcrystalline glass product. Further preferably, the total content of lithium disilicate and petalite crystalline phases accounts for 55-75% of the weight percentage of the microcrystalline glass product. Even more preferably, the total content of lithium disilicate and petalite crystalline phases accounts for 55-70% of the weight percentage of the microcrystalline glass product.

(15) According to any one of (1) to (6) of the glass-ceramic product, the weight percentage of the lithium disilicate crystalline phase in the glass-ceramic product is 15-40%, preferably the weight percentage of the lithium disilicate crystalline phase in the glass-ceramic product is 20-35%, and more preferably the weight percentage of the lithium disilicate crystalline phase in the glass-ceramic product is 25-35%; and/or the weight percentage of the petalite crystalline phase in the glass-ceramic product is 30-55%, preferably the weight percentage of the petalite crystalline phase in the glass-ceramic product is 35-55%, and more preferably the weight percentage of the petalite crystalline phase in the glass-ceramic product is 35-55%. The weight percentage of lithium feldspar crystal phase in the microcrystalline glass product is 35-50%; and/or the weight percentage of quartz and quartz solid solution crystal phase in the microcrystalline glass product is 5-25%, preferably the weight percentage of quartz and quartz solid solution crystal phase in the microcrystalline glass product is 7-20%; and/or the weight percentage of lithium silicate crystal phase in the microcrystalline glass product is 0-10%, preferably the weight percentage of lithium silicate crystal phase in the microcrystalline glass product is 0-7%, more preferably the weight percentage of lithium silicate crystal phase in the microcrystalline glass product is 0-5%.

(16) The microcrystalline glass product according to any one of (1) to (6), wherein the four-point bending strength of the microcrystalline glass product is 680 MPa or more, preferably 700 MPa or more, and more preferably 720 MPa or more; and/or the ion exchange layer depth of the microcrystalline glass product is 85 μm or more, preferably 100 μm or more, and more preferably 110 μm or more; and/or the surface stress of the microcrystalline glass product is 150 MPa or more, preferably 180 MPa or more, and more preferably 200 MPa or more; and/or the drop ball test height of the microcrystalline glass product is 1500 mm or more, preferably 1600 mm or more, and more preferably 1700 mm or more; and/or the fracture toughness of the microcrystalline glass product is 1 MPa·m ^1/2 or more, preferably 1.1 MPa·m ^1/2 or more, and more preferably 1.2 MPa·m ^1/2 or more; and/or the Vickers hardness of the microcrystalline glass product is 750 kgf/mm ² or more, and preferably 780 kgf/mm ² or more, more preferably 800kgf/mm2 ^or more; and/or the crystallinity of the microcrystalline glass product is 55% or more, preferably 65% or more, more preferably 75% or more; and/or the grain size of the microcrystalline glass product is 35nm or less, preferably 30nm or less, more preferably 25nm or less.

(17) According to any one of the microcrystalline glass products described in (1) to (6), the haze of the microcrystalline glass product with a thickness of less than 1 mm is less than 0.2%, preferably less than 0.15%, and more preferably less than 0.12%; and/or the average transmittance of the microcrystalline glass product with a thickness of less than 1 mm at a wavelength of 400 to 800 nm is greater than 87%, preferably greater than 88%, and more preferably greater than 89%; and/or the transmittance of the microcrystalline glass product with a thickness of less than 1 mm at a wavelength of 550 nm is greater than 88%, preferably greater than 90%, and more preferably greater than 91%; and/or the average optical |B| value of the microcrystalline glass product with a thickness of less than 1 mm at 400 to 800 nm is less than 0.8, preferably less than 0.75, and more preferably less than 0.7; and/or the drop resistance of the microcrystalline glass product with a thickness of less than 1 mm is greater than 1700 mm, preferably greater than 1800 mm, and more preferably greater than 2000 mm.

(18) The microcrystalline glass product according to (17), wherein the thickness of the microcrystalline glass product is 0.2 to 1 mm, preferably 0.3 to 0.9 mm, more preferably 0.5 to 0.8 mm, and further preferably 0.55 mm, 0.6 mm, 0.68 mm, 0.7 mm, or 0.75 mm.

(19) Glass-ceramics, whose components, expressed in molar percentage, contain: SiO ₂ : 65-75%; Al ₂ O ₃ : 1-8%; Li ₂ O: 14-27%; P ₂ O ₅ +ZrO ₂ : 0.5-6%.

(20) The microcrystalline glass according to (19) is characterized in that its components, expressed in molar percentage, further contain: ZnO+MgO: 0-4%; and/or _Na2O : _0-3.5 %; and/or _B2O3 : 0-3%; and/or _K2O : 0-3%; and/or SrO: 0-3%; and/or BaO: 0-3%; and/or CaO: 0-3%; and/or _TiO2 : 0-3%; and/or _Y2O3 : _0-3 %; and/or clarifier: 0-1%.

(21) Glass-ceramics, whose components, expressed in molar percentage, are composed of _SiO2 : _65-75 %; _Al2O3 : 1-8%; Li2O _{: 14-27%; P2O5 + ZrO2} : 0.5-6% _; ZnO+MgO: 0-4%; Na2O _: 0-3.5%; B2O3: 0-3%; _K2O : _0-3 %; SrO: 0-3%; BaO _: 0-3%; CaO: _0-3 %; _TiO2 : 0-3%; _Y2O3 : 0-3%; and clarifier: 0-1%.

(22) Glass-ceramics, whose components, expressed in molar percentage, contain: SiO ₂ : 65-75%; Al ₂ O ₃ : 1-8%; Li ₂ O: 14-27%, wherein the crystal phase in the glass-ceramics contains lithium silicate, and/or quartz and quartz solid solution, and/or petalite.

(23) Glass-ceramics, comprising _SiO2 , _Al2O3 and _Li2O as essential components, _wherein the crystalline phase in the glass-ceramics comprises lithium disilicate and petalite, the total content of lithium disilicate and petalite having a higher weight percentage than other crystalline phases, and the haze of the glass-ceramics having a thickness of less than 1 mm is less than 0.2%.

(24) The glass-ceramics according to any one of (22) to (23), wherein the components, expressed in molar percentage, are: _SiO2 : 65-75%; _Al2O3 : _1-8 % _; Li2O _: 14-27%; _P2O5 +ZrO2: 0.5-6%; ZnO+MgO: 0-4%; _Na2O : 0-3.5%; B2O3: _0-3 %; K2O: _0-3 %; SrO: 0-3%; BaO: 0-3%; CaO: 0-3%; _TiO2 : _0-3 % _{; Y2O3} : 0-3%; _and a clarifier: 0-1%.

(25) The glass-ceramics according to any one of (19) to (24), wherein the components are expressed in molar percentage, wherein: (Li ₂ O + ZrO ₂ ) / (ZnO + MgO) is 10 or more, preferably (Li ₂ O + ZrO ₂ ) / (ZnO + MgO) is 12 to 45, more preferably (Li ₂ O + ZrO ₂ ) / (ZnO + MgO) is 13 to 40, and further preferably (Li ₂ O + ZrO ₂ ) / (ZnO + MgO) is 15 to 35.

(26) The glass-ceramics according to any one of (19) to (24), wherein the components are expressed in molar percentage, wherein: ( _B2O3 + _Na2O + _ZrO2 )/( _Al2O3 +MgO) is 0.05 to 1.5, preferably ( _{B2O3 + Na2O} + _ZrO2 )/( _Al2O3 + _MgO ) is 0.1 _to 1, more preferably ( _B2O3 + _{Na2O +ZrO2)/(Al2O3+MgO) is 0.15 to 0.8, and further preferably (B2O3 + Na2O + ZrO2 ) / ( Al2O3} +MgO) is _0.2 to 0.7 _.

(27) The glass-ceramics according to any one of (19) to (24) _, wherein the components are expressed in molar percentage, wherein: ( _SiO2 + _Li2O )/( _Al2O3 +ZnO+MgO) is 5 to 40, preferably ( _SiO2 + _Li2O )/( _Al2O3 +ZnO+MgO ₎ is 8 to 30, more preferably ( _SiO2 + _Li2O )/( _Al2O3 +ZnO+MgO ₎ is ₁₀ to 25, and further preferably ( _SiO2 + _Li2O )/( _Al2O3 +ZnO+MgO) is 11 to 20.

(28) The glass-ceramics _according to any one of (19) to (24), wherein the components are expressed in molar percentage, wherein: ( _SiO2 + _Al2O3 + _Li2O + _Na2O + _{ZrO2 )} /( _P2O5 +MgO) is ₃₀ to 90, preferably ( _SiO2 + _Al2O3 + _Li2O + _Na2O + _ZrO2 )/( _P2O5 +MgO) is 35 _to 80, more preferably ( _{SiO2 + Al2O3} + _Li2O + _Na2O + _ZrO2 )/( _P2O5 +MgO) is ₃₈ to 75, and further preferably ( _SiO2 + _Al2O3 + _Li2O + _Na2O + _ZrO2 )/( _P2O5 +MgO) is _{40 to} 70.

(29) The glass-ceramics according to any one of (19) to (24), wherein the components are expressed in molar percentage, wherein: (SiO ₂ +Al ₂ O ₃ )/(P ₂ O ₅ +ZrO ₂ ) is 12 to 75, preferably (SiO ₂ +Al ₂ O ₃ )/(P ₂ O ₅ +ZrO ₂ ) is 15 to 70, more preferably (SiO ₂ +Al ₂ O ₃ )/(P ₂ O ₅ +ZrO ₂ ) is 17 to 65, and further preferably (SiO ₂ +Al ₂ O ₃ )/(P ₂ O ₅ +ZrO ₂ ) is 20 to 60.

(30) The glass-ceramics according to any one of (19) to (24), wherein the components are expressed in molar percentages, wherein: SiO ₂ : 67-73%, preferably SiO ₂ : 68-72%; and/or Al ₂ O ₃ : 2-6.5%, preferably Al ₂ O ₃ : 3-6%; and/or Li ₂ O : 15.5-25%, preferably Li ₂ O : 17-23.5%; and/or ZnO+MgO: 0.1-4%, preferably ZnO+MgO: 0.2-3%, more preferably ZnO+MgO: 0.5-2%; and/or P ₂ O ₅ +ZrO ₂ : 1-4%, preferably P ₂ O ₅ +ZrO ₂ : 1.2-3%; and/or Na ₂ O: 0.5-3%, preferably Na ₂ O: 0.5-2.5%; and/or B ₂ O ₃ : 0.5-2.5%, preferably B ₂ O ₃ : 0.5-2%; and/or K ₂ O: 0-2%, preferably K ₂ O: 0-1.5%; and/or SrO: 0-2%, preferably SrO: 0-1%; and/or BaO: 0-2%, preferably BaO: 0-1%; and/or CaO: 0-2%, preferably CaO: 0-1%; and/or TiO ₂ : 0-2%, preferably TiO ₂ : 0-1%; and/or Y ₂ O ₃ : 0-2%, preferably Y ₂ O ₃ : 0-1%; and/or clarifier: 0-0.5%, preferably clarifier: 0-0.2%.

(31) The glass-ceramics according to any one of (19) to (24), wherein the components are expressed in molar percentage, wherein: ZnO: 0-2%, preferably ZnO: 0-1.5%, more preferably ZnO: 0-1%; and/or MgO: 0-4%, preferably MgO: 0-3%, more preferably MgO: 0-1.5%; and/or P ₂ O ₅ : 0-3%, preferably P ₂ O ₅ : 0.2-2%, more preferably P ₂ O ₅ : 0.4-1.5%, further preferably P ₂ O ₅ : 0.5-1%; and/or ZrO ₂ : 0-4%, preferably ZrO ₂ : 0.2-3.5%, more preferably ZrO ₂ : 0.5-3%, further preferably ZrO ₂ : 0.7-2.5%.

(32) The glass-ceramics according to any one of (19) to (24), wherein the crystalline phase in the glass-ceramics contains lithium silicate; and/or quartz and quartz solid solution; and/or petalite. Preferably, the crystalline phase in the glass-ceramics contains lithium disilicate and petalite, and the combined content of lithium disilicate and petalite has a higher weight percentage than other crystalline phases. More preferably, the combined content of lithium disilicate and petalite crystalline phases accounts for 50 to 80% of the weight percentage of the glass-ceramics. Further preferably, the combined content of lithium disilicate and petalite crystalline phases accounts for 55 to 75% of the weight percentage of the glass-ceramics. Even more preferably, the combined content of lithium disilicate and petalite crystalline phases accounts for 55 to 70% of the weight percentage of the glass-ceramics.

(33) According to any one of (19) to (24), the weight percentage of the lithium disilicate crystalline phase in the glass-ceramic is 15-40%, preferably the weight percentage of the lithium disilicate crystalline phase in the glass-ceramic is 20-35%, and more preferably the weight percentage of the lithium disilicate crystalline phase in the glass-ceramic is 25-35%; and/or the weight percentage of the petalite crystalline phase in the glass-ceramic is 30-55%, preferably the weight percentage of the petalite crystalline phase in the glass-ceramic is 35-55%, and more preferably The weight percentage of petalite crystal phase in the microcrystalline glass is 35-50%; and/or the weight percentage of quartz and quartz solid solution crystal phase in the microcrystalline glass is 5-25%, preferably the weight percentage of quartz and quartz solid solution crystal phase in the microcrystalline glass is 7-20%; and/or the weight percentage of lithium silicate crystal phase in the microcrystalline glass is 0-10%, preferably the weight percentage of lithium silicate crystal phase in the microcrystalline glass is 0-7%, more preferably the weight percentage of lithium silicate crystal phase in the microcrystalline glass is 0-5%.

(34) The microcrystalline glass according to any one of (19) to (24), wherein the crystallinity of the microcrystalline glass is above 55%, preferably above 65%, and more preferably above 75%; and/or the grain size of the microcrystalline glass is below 35 nm, preferably below 30 nm, and more preferably below 25 nm; and/or the ball drop height of the microcrystalline glass body is above 1800 mm, preferably above 1900 mm, and more preferably above 2000 mm; and/or the Vickers hardness of the microcrystalline glass is above 680 kgf/ ^mm2 , preferably above 700 kgf/ ^mm2 , and more preferably above 710 kgf/ ^mm2 ; and/or the thermal expansion coefficient of the microcrystalline glass is 60× ^10-7 /K to 90× ^10-7 /K; and/or the refractive index of the microcrystalline glass is 1.5250 to 1.5450.

(35) According to any one of the microcrystalline glass described in (19) to (24), the haze of the microcrystalline glass with a thickness of less than 1 mm is less than 0.2%, preferably less than 0.15%, and more preferably less than 0.12%; and/or the average transmittance of the microcrystalline glass with a thickness of less than 1 mm at a wavelength of 400 to 800 nm is greater than 87%, preferably greater than 88%, and more preferably greater than 89%; and/or the transmittance of the microcrystalline glass with a thickness of less than 1 mm at a wavelength of 550 nm is greater than 88%, preferably greater than 90%, and more preferably greater than 91%; and/or the average optical |B| value of the microcrystalline glass with a thickness of less than 1 mm at 400 to 800 nm is less than 0.8, preferably less than 0.75, and more preferably less than 0.7.

(36) The microcrystalline glass according to (35) has a thickness of 0.2 to 1 mm, preferably 0.3 to 0.9 mm, more preferably 0.5 to 0.8 mm, and further preferably 0.55 mm, 0.6 mm, 0.68 mm, 0.7 mm or 0.75 mm.

(37) A glass composition, wherein the components, expressed in molar percentage, include: SiO ₂ : 65-75%; Al ₂ O ₃ : 1-8%; Li ₂ O: 14-27%; P ₂ O ₅ + ZrO ₂ : 0.5-6%.

(38) The glass composition according to (37), which comprises, expressed in molar percentage _, the following: ZnO+MgO: 0-4%; and/or _Na2O : 0-3.5%; and/or _B2O3 : 0-3%; and/or _K2O : 0-3%; and/or SrO: 0-3%; and/or BaO: 0-3%; and/or CaO: 0-3%; and/or _TiO2 : 0-3%; and/or _Y2O3 : 0-3%; and/or a _fining agent: 0-1%.

(39) A glass composition, the components of which, expressed in molar percentage, are composed of _SiO2 : 65-75%; _Al2O3 : 1-8%; Li2O: _14-27 %; _P2O5 + ZrO2 _: 0.5-6% _; ZnO + MgO: 0-4%; _{Na2O :} 0-3.5%; _B2O3 : _0-3 %; _K2O : 0-3%; SrO: 0-3%; BaO: 0-3%; CaO: 0-3%; _TiO2 : 0-3%; _Y2O3 : 0-3%; _and a clarifier: 0-1%.

(40) The glass composition according to any one of (37) to (39), wherein the components are expressed in molar percentage, wherein: (Li ₂ O + ZrO ₂ ) / (ZnO + MgO) is 10 or more, preferably (Li ₂ O + ZrO ₂ ) / (ZnO + MgO) is 12 to 45, more preferably (Li ₂ O + ZrO ₂ ) / (ZnO + MgO) is 13 to 40, and further preferably (Li ₂ O + ZrO ₂ ) / (ZnO + MgO) is 15 to 35.

(41) The glass composition according to any one of (37) to (39), wherein the components are expressed in molar percentage: ( _B2O3 + _Na2O + _ZrO2 )/( _Al2O3 +MgO) is 0.05 to 1.5, preferably ( _{B2O3 + Na2O} + _ZrO2 )/ _{( Al2O3} +MgO) is 0.1 _to 1, more preferably ( _B2O3 + _{Na2O +ZrO2)/(Al2O3+MgO) is 0.15 to 0.8, and further preferably (B2O3 + Na2O + ZrO2 ) / ( Al2O3 +} MgO) is _0.2 to 0.7.

(42) The glass composition according to any one of (37) to (39) _, wherein the components are expressed in molar percentage _, wherein: ( _SiO2 + _Li2O )/( _Al2O3 + ZnO+MgO) is 5 to 40, preferably ( _SiO2 + _Li2O )/( _Al2O3 + ZnO+MgO) is 8 to 30, more preferably ( _SiO2 + _Li2O )/( _Al2O3 + ZnO+MgO) is 10 to 25, and further preferably ( _SiO2 + _Li2O )/( _Al2O3 + _ZnO +MgO) is 11 _to 20.

(43) The glass composition _according to any one of (37) to (39), wherein the components are expressed in molar percentage, wherein: ( _SiO2 + _Al2O3 + _Li2O + _Na2O + _ZrO2 ) / ( _P2O5 + MgO) is ₃₀ to 90, preferably ( _SiO2 + _Al2O3 + _Li2O + _Na2O + _ZrO2 ) / ( _{P2O5 + MgO) is 35 to 80, more preferably (SiO2 + Al2O3 + Li2O + Na2O + ZrO2) / (P2O5 + MgO ) is 38 to 75 ,} and further preferably ( _SiO2 + _Al2O3 + _Li2O + _Na2O + _ZrO2 ) / ( _P2O5 + MgO) is _{40 to 70 .}

(44) The glass composition according to any one of (37) to ( ₃₉ ), wherein the components are expressed in molar percentage, wherein: ( _SiO2 + _Al2O3 )/( _P2O5 + _ZrO2 ) is _{12 to 75, preferably (SiO2 + Al2O3)/(P2O5 + ZrO2) is 15 to 70, more preferably (SiO2 + Al2O3 ) / ( P2O5 + ZrO2 ) is 17 to 65 ,} and further preferably ( _SiO2 + _Al2O3 )/( _P2O5 + _ZrO2 ) is ₂₀ to 60.

(45) The glass composition according to any one of (37) to (39), wherein the components are expressed in molar percentages, wherein: _SiO2 : 67-73%, preferably _SiO2 : 68-72%; and/or _{Al2O3 :} 2-6.5% _, preferably _Al2O3 : 3-6%; and/or _Li2O : 15.5-25%, preferably _Li2O : 17-23.5%; and/or ZnO+MgO: 0.1-4%, preferably ZnO+MgO: 0.2-3%, more preferably ZnO+MgO: 0.5-2%; and/or _P2O5 + _ZrO2 : 1-4%, preferably _P2O5 + _ZrO2 : 1.2-3%; and/or _Na2O : 0.5-3%, preferably _Na2O : 0.5-2.5%; and/or _B2O3 : 0.1-4%, preferably _ZnO+ MgO: 0.2-3%, more preferably ZnO+ _MgO : _0.5-2 %; : 0.5-2.5%, preferably B ₂ O ₃ : 0.5-2%; and/or K ₂ O: 0-2%, preferably K ₂ O: 0-1.5%; and/or SrO: 0-2%, preferably SrO: 0-1%; and/or BaO: 0-2%, preferably BaO: 0-1%; and/or CaO: 0-2%, preferably CaO: 0-1%; and/or TiO ₂ : 0-2%, preferably TiO ₂ : 0-1%; and/or Y ₂ O ₃ : 0-2%, preferably Y ₂ O ₃ : 0-1%; and/or clarifier: 0-0.5%, preferably clarifier: 0-0.2%.

(46) A glass composition according to any one of (37) to (39), wherein the components are expressed in molar percentage, wherein: ZnO: 0-2%, preferably ZnO: 0-1.5%, more preferably ZnO: 0-1%; and/or MgO: 0-4%, preferably MgO: 0-3%, more preferably MgO: 0-1.5%; and/or P ₂ O ₅ : 0-3%, preferably P ₂ O ₅ : 0.2-2%, more preferably P ₂ O ₅ : 0.4-1.5%, further preferably P ₂ O ₅ : 0.5-1%; and/or ZrO ₂ : 0-4%, preferably ZrO ₂ : 0.2-3.5%, more preferably ZrO ₂ : 0.5-3%, further preferably ZrO ₂ : 0.7-2.5%.

(47) The glass composition according to any one of (37) to (39), wherein the thermal expansion coefficient of the glass composition is 55×10 ^-7 /K to 65×10 ^-7 /K, and/or the refractive index is 1.5100 to 1.5300.

(48) A glass cover plate, made of the microcrystalline glass product described in any one of (1) to (18), and/or made of the microcrystalline glass described in any one of (19) to (36), and/or made of the glass composition described in any one of (37) to (47).

(49) Glass components are made of the microcrystalline glass products described in any one of (1) to (18), and/or made of the microcrystalline glass described in any one of (19) to (36), and/or made of the glass composition described in any one of (37) to (47).

(50) A display device comprising the microcrystalline glass product described in any one of (1) to (18), and/or the microcrystalline glass described in any one of (19) to (36), and/or the glass composition described in any one of (37) to (47), and/or the glass cover described in (48), and/or the glass component described in (49).

(51) An electronic device comprising a glass-ceramic product as described in any one of (1) to (18), and/or a glass-ceramic product as described in any one of (19) to (36), and/or a glass composition as described in any one of (37) to (47), and/or a glass cover as described in (48), and/or a glass component as described in (49).

(52) A method for manufacturing a microcrystalline glass product as described in any one of (1) to (18), the method comprising the following steps: generating a glass composition, subjecting the glass composition to a crystallization process to form a microcrystalline glass, and then subjecting the microcrystalline glass to a chemical strengthening process to form a microcrystalline glass product.

(53) According to the method for manufacturing a microcrystalline glass product described in (52), a glass composition is manufactured into a glass molded body, and then the glass molded body is subjected to a crystallization process to form a microcrystalline glass, and then the microcrystalline glass is subjected to a chemical strengthening process to form a microcrystalline glass product, or microcrystalline glass is manufactured into a microcrystalline glass molded body, and then the microcrystalline glass molded body is subjected to a chemical strengthening process to form a microcrystalline glass product.

(54) According to the method for manufacturing microcrystalline glass products described in (52), the crystallization process includes the following steps: heating to a specified crystallization treatment temperature, maintaining the temperature for a certain period of time after reaching the crystallization treatment temperature, and then cooling down, the crystallization treatment temperature is 600-750°C, preferably 650-720°C, and the holding time at the crystallization treatment temperature is 0-8 hours, preferably 1-6 hours.

(55) According to the manufacturing method of microcrystalline glass products described in (52), the crystallization process includes the following steps: performing a nucleation process at a first temperature, and then performing a crystal growth process at a second temperature, the first temperature is 470-600°C, and the holding time at the first temperature is 0-24 hours, preferably 2-15 hours, and the second temperature is 600-750°C, and the holding time at the second temperature is 0-10 hours, preferably 0.5-6 hours.

(56) According to the manufacturing method of microcrystalline glass products described in (52), the crystallization process includes the following steps: performing a nucleation process at a first temperature, and then performing a crystal growth process at a second temperature and a third temperature, wherein the first temperature is 470-550°C, and the holding time at the first temperature is 0-24 hours, preferably 2-15 hours, the second temperature is 570-630°C, and the holding time at the second temperature is 0-10 hours, preferably 0.5-6 hours, and the third temperature is 650-750°C, and the holding time at the third temperature is 0-10 hours, preferably 0.5-6 hours.

(57) According to the method for manufacturing microcrystalline glass products described in (52), the chemical strengthening process includes: the microcrystalline glass is immersed in a salt bath of molten Na salt at a temperature of 320°C to 470°C for 6 to 20 hours, preferably in the temperature range of 360°C to 460°C, and the preferred time range is 8 to 13 hours; and/or the microcrystalline glass is immersed in a salt bath of molten K salt at a temperature of 340°C to 450°C for 1 to 24 hours, preferably in the time range of 2 to 10 hours; and/or the microcrystalline glass is immersed in a mixed salt bath of molten K salt and molten Na salt at a temperature of 340°C to 500°C for 1 to 24 hours, preferably in the time range of 2 to 10 hours.

(58) A method for manufacturing microcrystalline glass as described in any one of (19) to (36), the method comprising the following steps: generating a glass composition and then subjecting the glass composition to a crystallization process to form microcrystalline glass.

(59) According to the method for manufacturing microcrystalline glass described in (58), the glass composition is manufactured into a glass molded body, and then the glass molded body is formed into microcrystalline glass through a crystallization process.

(60) According to the method for manufacturing microcrystalline glass described in (58), the crystallization process includes the following steps: heating to a specified crystallization treatment temperature, maintaining the temperature for a certain period of time after reaching the crystallization treatment temperature, and then cooling down, the crystallization treatment temperature is 600-750°C, preferably 650-720°C, and the holding time at the crystallization treatment temperature is 0-8 hours, preferably 1-6 hours.

(61) According to the method for manufacturing microcrystalline glass as described in (58), the crystallization process includes the following steps: performing a nucleation process at a first temperature, and then performing a crystal growth process at a second temperature, the first temperature is 470-600°C, and the holding time at the first temperature is 0-24 hours, preferably 2-15 hours, and the second temperature is 600-750°C, and the holding time at the second temperature is 0-10 hours, preferably 0.5-6 hours.

(62) According to the method for manufacturing microcrystalline glass as described in (58), the crystallization process includes the following steps: performing a nucleation process at a first temperature, and then performing a crystal growth process at a second temperature and a third temperature, wherein the first temperature is 470-550°C, and the holding time at the first temperature is 0-24 hours, preferably 2-15 hours, the second temperature is 570-630°C, and the holding time at the second temperature is 0-10 hours, preferably 0.5-6 hours, and the third temperature is 650-750°C, and the holding time at the third temperature is 0-10 hours, preferably 0.5-6 hours.

The beneficial effects of the present invention are as follows: through reasonable component design, the microcrystalline glass and microcrystalline glass products obtained by the present invention have excellent mechanical properties and optical properties, and are suitable for electronic devices or display devices.

DETAILED DESCRIPTION

The glass-ceramics and glass-ceramics products of the present invention are materials having a crystalline phase and a glass phase, which are different from amorphous solids. The crystalline phase of the glass-ceramics and glass-ceramics products can be identified by the peak angle appearing in the X-ray diffraction pattern of X-ray diffraction analysis and/or measured by TEMEDX.

After repeated experiments and studies, the inventors of the present invention have obtained the microcrystalline glass or microcrystalline glass products of the present invention at a relatively low cost by regulating the content and content ratio of the specific components constituting microcrystalline glass and microcrystalline glass products to specific values and precipitating specific crystalline phases.

In the glass-ceramics or glass-ceramics products of the present invention, the crystalline phase contains lithium silicate; and/or quartz and quartz solid solution; and/or petalite. The lithium silicate crystalline phase of the present invention contains lithium monosilicate and/or lithium disilicate. In the present invention, the crystalline phase is sometimes also referred to as crystal.

In some embodiments of the present invention, the crystalline phase in the microcrystalline glass or microcrystalline glass products contains lithium disilicate, and the content of lithium disilicate has a higher weight percentage than other crystalline phases, so that the microcrystalline glass or microcrystalline glass products of the present invention have excellent performance.

In some embodiments of the present invention, the crystalline phase in the microcrystalline glass or microcrystalline glass products contains petalite, and the content of petalite has a higher weight percentage than other crystalline phases, so that the microcrystalline glass or microcrystalline glass products of the present invention have excellent performance.

In some embodiments of the present invention, the crystalline phase in the microcrystalline glass or microcrystalline glass products contains lithium silicate, and the content of lithium silicate has a higher weight percentage than other crystalline phases, so that the microcrystalline glass or microcrystalline glass products of the present invention have excellent performance.

In some embodiments of the present invention, the crystalline phase in the microcrystalline glass or microcrystalline glass products contains quartz and quartz solid solution, and the content of quartz and quartz solid solution has a higher weight percentage than other crystalline phases, so that the microcrystalline glass or microcrystalline glass products of the present invention have excellent performance.

In some embodiments of the present invention, the crystalline phase in the microcrystalline glass or microcrystalline glass products contains lithium disilicate and petalite, and the combined content of lithium disilicate and petalite has a higher weight percentage than other crystalline phases, so that the microcrystalline glass or microcrystalline glass products of the present invention have excellent performance.

In some embodiments of the present invention, the crystalline phase in the microcrystalline glass or microcrystalline glass products contains lithium silicate and petalite, and the combined content of lithium silicate and petalite has a higher weight percentage than other crystalline phases, so that the microcrystalline glass or microcrystalline glass products of the present invention have excellent performance.

In some embodiments of the present invention, the crystalline phase in the microcrystalline glass or microcrystalline glass products contains lithium disilicate, quartz and quartz solid solution, and the combined content of lithium disilicate, quartz and quartz solid solution has a higher weight percentage than other crystalline phases, so that the microcrystalline glass or microcrystalline glass products of the present invention have excellent performance.

In some embodiments of the present invention, the crystalline phases in the microcrystalline glass or microcrystalline glass products contain petalite, quartz and quartz solid solution, and the combined content of petalite, quartz and quartz solid solution has a higher weight percentage than other crystalline phases, so that the microcrystalline glass or microcrystalline glass products of the present invention have excellent performance.

In some embodiments, the weight percentage of the lithium disilicate crystalline phase in the glass-ceramic or glass-ceramic product is 15-40%. In some embodiments, the weight percentage of the lithium disilicate crystalline phase in the glass-ceramic or glass-ceramic product is 20-35%. In some embodiments, the weight percentage of the lithium disilicate crystalline phase in the glass-ceramic or glass-ceramic product is 25-35%.

In some embodiments, the weight percentage of quartz and quartz solid solution crystal phase in the glass-ceramic or glass-ceramic product is 5-25%. In some embodiments, the weight percentage of quartz and quartz solid solution crystal phase in the glass-ceramic or glass-ceramic product is 7-20%.

In some embodiments, the weight percentage of the petalite crystalline phase in the glass-ceramic or glass-ceramic product is 30-55%. In some embodiments, the weight percentage of the petalite crystalline phase in the glass-ceramic or glass-ceramic product is 35-55%. In some embodiments, the weight percentage of the petalite crystalline phase in the glass-ceramic or glass-ceramic product is 35-50%.

In some embodiments, the weight percentage of the lithium silicate crystal phase in the glass-ceramic or glass-ceramic product is 0-10%. In some embodiments, the weight percentage of the lithium silicate crystal phase in the glass-ceramic or glass-ceramic product is 0-7%. In some embodiments, the weight percentage of the lithium silicate crystal phase in the glass-ceramic or glass-ceramic product is 0-5%.

In some embodiments, the total content of lithium disilicate and petalite crystalline phases is 50-80% by weight of the glass-ceramic or glass-ceramic product. In some embodiments, the total content of lithium disilicate and petalite crystalline phases is 55-75% by weight of the glass-ceramic or glass-ceramic product. In some embodiments, the total content of lithium disilicate and petalite crystalline phases is 55-70% by weight of the glass-ceramic or glass-ceramic product.

The following is an explanation of the scope of each component (ingredient) of the glass composition, glass-ceramics, and glass-ceramics products of the present invention. In this specification, unless otherwise specified, the content of each component is expressed in molar percentage (mol%) relative to the total amount of the glass composition, glass-ceramics, or glass-ceramics product material converted into an oxide composition. Here, the "composition converted into oxides" refers to the case where oxides, complex salts, hydroxides, etc. used as raw materials for the glass composition, glass-ceramics, or glass-ceramics products of the present invention decompose and transform into oxides when melted, and the total molar amount of the oxide material is taken as 100%. In addition, in this specification, when it is simply referred to as glass, it is a glass composition before crystallization, and a glass composition after crystallization is referred to as glass-ceramics, and a glass-ceramics product refers to chemically strengthened glass-ceramics.

Unless otherwise indicated in specific cases, the numerical ranges listed herein include upper and lower limits, and "above" and "below" include the endpoints, as well as all integers and fractions within the range, without limitation to the specific values listed when the range is defined. The term "about" as used herein means that the formula, parameters and other quantities and features are not and need not be exact, and may be approximate and/or larger or lower if necessary, reflecting tolerances, conversion factors and measurement errors, etc. "And/or" as used herein is inclusive, for example, "A; and/or B" means only A, or only B, or both A and B.

_SiO2 is the basic component of the glass composition, glass-ceramics and glass-ceramics products of the present invention, and is one of the main components of the crystalline phase of glass-ceramics and glass-ceramics products. If the content of _SiO2 is less than 65%, the crystals formed in glass-ceramics and glass-ceramics products will become less and the crystals will easily become coarser, affecting the drop ball test height and haze of glass-ceramics and glass-ceramics products. Therefore, the lower limit of the _SiO2 content is 65%, preferably 67%, and more preferably 68%. On the other hand, if the _SiO2 content exceeds 75%, the glass melting temperature is high, the material is difficult to smelt, and it is not easy to shape during the manufacturing process, affecting the uniformity of the glass. Therefore, the upper limit of the _SiO2 content is 75%, preferably 73%, and more preferably 72%. In some embodiments, SiO2 may be comprised at about 65%, 65.5%, 66%, 66.5%, 67%, 67.5%, 68%, 68.5%, 69%, 69.5%, 70%, 70.5%, 71%, _71.5 %, 72%, 72.5%, 73%, 73.5%, 74%, 74.5%, 75%.

Al ₂ O ₃ is a component that forms a glass network structure and is one of the components that form a petalite crystal phase. It is beneficial to the chemical strengthening of glass and increases the drop ball test height of microcrystalline glass products. However, if its content is less than 1%, the above effect is not good. Therefore, the lower limit of the Al ₂ O ₃ content is 1%, preferably 2%, and more preferably 3%. On the other hand, if the Al ₂ O ₃ content exceeds 8%, the meltability and devitrification resistance of the glass are reduced, and the crystals tend to increase during glass crystallization, reducing the strength of microcrystalline glass and microcrystalline glass products. Therefore, the upper limit of the Al ₂ O ₃ content is 8%, preferably 6.5%, and more preferably 6%. In some embodiments, about 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8% Al ₂ O ₃ may be included.

_Li2O is an essential component for the formation of crystals in the glass-ceramics and glass-ceramics products of the present invention. It is also an essential component for participating in chemical strengthening and improving the mechanical properties of glass-ceramics products. If the _Li2O content is less than 14%, the crystal content in the glass-ceramics and glass-ceramics products is insufficient, which reduces the strength of the glass-ceramics and glass-ceramics products. Therefore, the lower limit of the _Li2O content is 14%, preferably 15.5%, and more preferably 17%. On the other hand, if too much _Li2O is contained, the haze of the glass-ceramics and glass-ceramics products increases. Therefore, the upper limit of the _Li2O content is 27%, preferably 25%, and more preferably 23.5%. In some embodiments, about 14%, 14.5%, 15%, 15.5%, 16%, 16.5%, 17%, 17.5%, 18%, 18.5%, 19%, 19.5%, 20%, 20.5%, 21%, 21.5%, 22%, 22.5%, 23%, 23.5%, 24%, 24.5%, 25%, 25.5%, 26%, 26.5%, 27% _Li2O may be included.

ZnO and MgO can promote the formation of quartz and quartz solid solution in glass-ceramics. If the total content of ZnO+MgO is too high, the haze of glass-ceramics and glass-ceramics products will increase. Therefore, ZnO+MgO is limited to less than 4%. If ZnO+MgO is too low, glass-ceramics and glass-ceramics products cannot form quartz and quartz solid solution under low haze conditions, which is not conducive to achieving the excellent mechanical properties of the glass-ceramics and glass-ceramics products of the present invention. Therefore, it is preferred that ZnO+MgO is 0.1-4%, more preferably ZnO+MgO is 0.2-3%, and further preferably ZnO+MgO is 0.5-2%. In some embodiments, the content of ZnO is preferably 0-2%, more preferably 0-1.5%, and further preferably 0-1%. In some embodiments, the content of MgO is preferably 0-4%, more preferably 0-3%, and further preferably 0-1.5%. In some embodiments, the value of ZnO+MgO may be 0%, greater than 0%, 0.01%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%. In some embodiments, about 0%, greater than 0%, 0.01%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.5%, 2% ZnO may be included. In some embodiments, about 0%, greater than 0%, 0.01%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4% MgO may be included.

The inventors have found through a large number of experimental studies that in some embodiments of the present invention, the ratio of the total content of Li ₂ O and ZrO ₂ (Li ₂ O + ZrO ₂ ) / (ZnO + MgO) between the total content of ZnO and MgO (ZnO + MgO) (Li ₂ O + ZrO ₂ ) / (ZnO + MgO) is controlled to be above 10, which can reduce the haze of microcrystalline glass and microcrystalline glass products and improve the light transmittance. Therefore, it is preferred that (Li ₂ O + ZrO ₂ ) / (ZnO + MgO) is above 10, and more preferably (Li ₂ O + ZrO ₂ ) / (ZnO + MgO) is 12 to 45. Furthermore, by controlling (Li ₂ O + ZrO ₂ ) / (ZnO + MgO) within the range of 13 to 40, the chemical strengthening performance of microcrystalline glass can be further improved, the depth of the ion exchange layer and the surface stress of the microcrystalline glass products can be increased, and the four-point bending strength of the microcrystalline glass products can be improved. Therefore, it is more preferred that ( _Li2O + _ZrO2 )/(ZnO+MgO) is 13 to 40, and it is even more preferred that ( _Li2O + _ZrO2 )/(ZnO+MgO) is 15 to 35. In some embodiments, the value of _Li2O /(ZnO+MgO) may be 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45.

In some embodiments, by controlling (SiO ₂ +Li ₂ O)/(Al ₂ O ₃ +ZnO+MgO) within the range of 5 to 40, it is beneficial to improve the drop ball test height and fracture toughness of microcrystalline glass and microcrystalline glass products. Therefore, it is preferred that (SiO ₂ +Li ₂ O)/(Al ₂ O ₃ +ZnO+MgO) is 5 to 40, and more preferably (SiO ₂ +Li ₂ O)/(Al ₂ O ₃ +ZnO+MgO) is 8 to 30. Furthermore, by controlling (SiO ₂ +Li ₂ O)/(Al ₂ O ₃ +ZnO+MgO) within the range of 10 to 25, it is also beneficial to reduce the haze of microcrystalline glass and microcrystalline glass products and improve the light transmittance. Therefore, it is more preferred that ( _SiO2 + _Li2O )/( _Al2O3 +ZnO+MgO) is 10 to 25, and it is even more preferred that ( _SiO2 + _Li2O )/( _Al2O3 +ZnO+MgO) is 11 to 20. In some embodiments, the value of ( _SiO2 + _Li2O )/( _{Al2O3 +} ZnO+MgO) may be 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, ₃₂ , ₃₃ , 34, 35, 36, 37, 38, 39, 40.

_P2O5 and _ZrO2 have a nucleation effect. When their combined content _P2O5 + _ZrO2 is above 0.5%, it is beneficial _to form the desired crystals of the present invention, so as to achieve the excellent mechanical _and optical properties of the glass- _ceramics and glass-ceramics products of the present invention. If their combined content _P2O5 + _ZrO2 exceeds 6%, the grain size in the glass-ceramics or glass-ceramics products becomes larger, the haze and transmittance of the glass-ceramics and glass-ceramics products increase, _and the mechanical properties decrease. Therefore, _P2O5 + _ZrO2 is _0.5-6 %, preferably _P2O5 + _ZrO2 is 1-4%, and more preferably _P2O5 + _ZrO2 is _1.2-3 %. In some embodiments, the value of P ₂ O ₅ +ZrO ₂ may be 0.5%, 1%, 1.2%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%.

In some embodiments, the ratio _{of the total content of SiO2 and Al2O3 (SiO2+Al2O3) to the total content of P2O5 and ZrO2 ( P2O5 + ZrO2 ) ( SiO2 + Al2O3 ) / ( P2O5} + _ZrO2 ) is controlled within the range _{of 12 to 75, which can improve the crystallinity of the microcrystalline glass and microcrystalline glass products and reduce the grain size. Therefore, preferably (SiO2 + Al2O3 )} /( _P2O5 + _ZrO2 ) is ₁₂ to ₇₅ , and more preferably ( _SiO2 + _Al2O3 )/( _P2O5 + _ZrO2 ) is _{15 to} 70 _. Furthermore, by controlling (SiO ₂ +Al ₂ O ₃ )/(P ₂ O ₅ +ZrO ₂ ) within the range of 17 to 65, _the fracture toughness and drop resistance of the microcrystalline glass products can be further improved, and the drop ball test height of the microcrystalline glass _and microcrystalline glass products can _be increased.

(P ₂ O ₅ +ZrO ₂ ) is 17-65, and more preferably (SiO ₂ +Al ₂ O ₃ )/(P ₂ O ₅ +ZrO ₂ ) is 20-60. In some embodiments, the value of ( _SiO2 + _Al2O3 )/( _P2O5 + _ZrO2 ) may be 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, ₆₄ , 65, 66, 67, 68, 69 _, 70, 71, 72, 73, 74, 75.

_P2O5 can form crystal nuclei in glass, promote crystal formation, improve the strength of microcrystalline glass and microcrystalline glass products, and help reduce the haze of microcrystalline glass and microcrystalline glass products. On the other hand, if too _{much P2O5} is contained _, it is easy to cause devitrification during the production process of the glass composition, increasing the difficulty of glass molding. Therefore, the content range _{of P2O5} is preferably 0-3%, more preferably 0.2-2%, further preferably 0.4-1.5%, and further preferably 0.5-1%. In some embodiments, about 0%, greater than 0%, 0.01%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.5%, 2%, 2.5%, 3% of _{P2O5 may be included} .

_ZrO2 has the function of crystallization and precipitation to form crystal nuclei, which can refine the grains and reduce the haze of microcrystalline glass and microcrystalline glass products. On the other hand, if too much _ZrO2 is contained, the haze of microcrystalline glass and microcrystalline glass products will increase. Therefore, the content of _ZrO2 is preferably 0-4%, more preferably 0.2-3.5%, further preferably 0.5-3%, and further preferably 0.7-2.5%. In some embodiments, about 0%, greater than 0%, 0.01%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4% _{ZrO2 may} be included.

_Na2O can reduce the haze of glass-ceramics and glass-ceramics products, increase the glass phase in glass-ceramics, and facilitate the hot bending of glass-ceramics. However, if too much _Na2O is contained, it will cause the crystals in glass-ceramics and glass-ceramics products to coarsen, which will lead to the deterioration of the haze and transmittance of glass-ceramics and glass-ceramics products. Therefore, the content range of _Na2O is 0-3.5%, preferably 0.5-3%, and more preferably 0.5-2.5%. In some embodiments, about 0%, greater than 0%, 0.01%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5% of _Na2O may be included.

In some embodiments, the |B| value _and haze of the glass-ceramics and glass-ceramics products can be reduced by controlling ( _SiO2 + _Al2O3 + _Li2O + _Na2O + _ZrO2 )/( _P2O5 +MgO) within the range of 30 to _90. Therefore, ( _SiO2 + _Al2O3 + _Li2O + _Na2O +ZrO2)/( _P2O5 +MgO) is preferably 30 to 90, and ( _SiO2 + _Al2O3 + _Li2O + _Na2O + _{ZrO2 )} /( _P2O5 + _MgO ) is more preferably _{35 to} 80 _. Furthermore, by controlling (SiO ₂ +Al ₂ O ₃ +Li ₂ O+Na ₂ O+ZrO ₂ )/(P ₂ O ₅ +MgO) within the range of 38 to 75, the four-point bending strength and Vickers hardness of the microcrystalline glass and microcrystalline glass products can be improved, and the ion exchange layer depth and surface stress of the microcrystalline glass products can be improved. Therefore, it is further preferred that (SiO ₂ +Al ₂ O ₃ +Li ₂ O+Na ₂ O+ZrO ₂ )/(P ₂ O ₅ +MgO) is 38 to 75, and it is further preferred that (SiO ₂ +Al ₂ O ₃ +Li ₂ O+Na ₂ O+ZrO ₂ )/(P ₂ O ₅ +MgO) is 40 to 70. In some embodiments,

The value of ( _SiO2 + _Al2O3 + _Li2O + _Na2O +ZrO2)/( _P2O5 +MgO) can be 30, 31, ₃₂ , 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, _{54, 55} , ₅₆ , 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90.

_B2O3 does not participate in the formation of crystals in glass, but can increase the glass phase in microcrystalline glass, which is beneficial to the hot bending of microcrystalline glass. However, if too _{much B2O3} is contained, it will cause the grains to grow rapidly, _which is difficult to control during the crystallization process. Therefore, the content of _B2O3 ranges from 0 to 3%, preferably from 0.5 to 2.5%, and more preferably from 0.5 to 2%. In some embodiments, about 0%, _greater than 0%, 0.01%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.5%, 2%, 2.5%, 3% _{B2O3 may} be included.

In some embodiments, by controlling (B ₂ O ₃ +Na ₂ O+ZrO ₂ )/(Al ₂ O ₃ +MgO) within the range of 0.05 to 1.5, the Vickers hardness of glass-ceramics and glass-ceramics products can be increased, and the grain size of glass-ceramics and glass-ceramics products can be reduced. Therefore, preferably (B ₂ O ₃ +Na ₂ O+ZrO ₂ )/(Al ₂ O ₃ +MgO) is 0.05 to 1.5, and more preferably (B ₂ O ₃ +Na ₂ O+ZrO ₂ )/(Al ₂ O ₃ +MgO) is 0.1 to 1. Furthermore, by controlling (B ₂ O ₃ +Na ₂ O+ZrO ₂ )/(Al ₂ O ₃ +MgO) to 0.15 to 0.8, the crystallinity and drop resistance of glass-ceramics and glass-ceramics products can be further improved. Therefore, ( _B2O3 + _Na2O + _ZrO2 ) _/ ( _Al2O3 +MgO) is more preferably _0.15 to 0.8, _and ( _B2O3 + _Na2O + _ZrO2 )/( _Al2O3 +MgO) is still more preferably _0.2 to 0.7. In some embodiments, the value of ( _B2O3 + _Na2O + _ZrO2 )/( _Al2O3 +MgO) may be 0.05, 0.1, _0.15 , 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, 1, 1.05, 1.1, 1.15, 1.2, 1.25, 1.3, 1.35, 1.4, _1.45 , 1.5.

_K2O can reduce the viscosity of glass and promote the formation of crystals during heat treatment. However, if _K2O is contained in excess, it is easy to cause coarsening of glass crystals and reduce the transmittance and drop test height of microcrystalline glass and microcrystalline glass products. Therefore, the content of _K2O is 3% or less, preferably 2% or less, and more preferably 1.5% or less. In some embodiments, about 0%, greater than 0%, 0.01%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.5%, 2%, 2.5%, 3% _K2O may be included.

SrO is an optional component that improves the low temperature melting property of glass and inhibits crystallization during glass forming, but excessive content is not conducive to glass forming. Therefore, the content of SrO in the present invention ranges from 0 to 3%, preferably from 0 to 2%, more preferably from 0 to 1%, and further preferably does not contain SrO. In some embodiments, about 0%, greater than 0%, 0.01%, 0.05%, 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3% SrO may be included.

BaO is an optional component that helps improve the glass-forming properties of glass. Too much BaO is not conducive to glass forming. Therefore, the content of BaO in the present invention ranges from 0 to 3%, preferably from 0 to 2%, more preferably from 0 to 1%, and more preferably does not contain BaO. In some embodiments, about 0%, greater than 0%, 0.01%, 0.05%, 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3% BaO may be included.

CaO can increase the hardness of glass. When the content is too high, the glass tends to milk during molding. Therefore, the content of CaO in the present invention is in the range of 0-3%, preferably 0-2%, more preferably 0-1%, and more preferably no CaO. In some embodiments, the CaO may be contained in an amount of about 0%, greater than 0%, 0.01%, 0.05%, 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%.

_TiO2 is an optional component that helps to lower the melting temperature of glass and improve chemical stability. In the present invention, by containing less than 3% of _TiO2 , the crystallization process of glass can be easily controlled. Preferably, the content of _TiO2 is less than 2%, and more preferably less than 1%. In some embodiments, it is further preferred that _TiO2 is not contained. In some embodiments, about 0%, greater than 0%, 0.01%, 0.05%, 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3% of _TiO2 may be contained.

Y ₂ O ₃ can reduce the difficulty of melting glass, reduce phase separation in glass, and reduce the haze and |B| value of microcrystalline glass and microcrystalline glass products. If the Y ₂ O ₃ content is too much, it is difficult to form crystals during glass crystallization, and the crystallinity of microcrystalline glass and microcrystalline glass products decreases. Therefore, the upper limit of the Y ₂ O ₃ content is 3%, preferably 2%, more preferably 1%, and more preferably no Y ₂ O _3. In some embodiments, about 0%, greater than 0%, 0.01%, 0.05%, 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3% Y ₂ O ₃ may be included.

In some embodiments, the glass, glass-ceramic or glass-ceramic product may further include 0-1% of a clarifier to improve the defoaming ability of the glass, glass-ceramic or glass-ceramic product. Such clarifiers include, but are not limited to, one or more of Sb ₂ O ₃ , SnO ₂ , SnO and CeO ₂ , preferably Sb ₂ O ₃ as a clarifier. When the above clarifiers are present alone or in combination, the upper limit of their content is preferably 0.5%, more preferably 0.2%. In some embodiments, the content of one or more of the above clarifiers is about 0%, greater than 0%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%.

In order to make the glass, glass-ceramics or glass-ceramics products of the present invention obtain the desired excellent properties such as mechanical properties, optical properties, production performance and chemical strengthening performance, in some embodiments of the present invention, it is preferred that F is not contained. PbO and As ₂ O ₃ are toxic substances, and even a small amount of addition does not meet the requirements of environmental protection. Therefore, in some embodiments of the present invention, PbO and As ₂ O ₃ are preferably not contained.

In some embodiments of the present invention, a colored glass composition, glass-ceramic or glass-ceramic product can be prepared by containing a colorant, so that the glass composition, glass-ceramic or glass-ceramic product can present different colors. In some embodiments, an antimicrobial component can be added to the glass composition, glass-ceramic or glass-ceramic product. The glass-ceramic or glass-ceramic product described herein can be used in applications such as kitchen or dining countertops, where exposure to harmful bacteria is likely. The antimicrobial components that can be added to the glass composition, glass-ceramic or glass-ceramic product include but are not limited to Ag, AgO, Cu, CuO, Cu ₂ O, etc. In some embodiments, the content of the above antimicrobial components alone or in combination is less than 2%, preferably less than 1%.

The "does not contain" and "0%" recorded in this article mean that the compound, molecule or element is not intentionally added as a raw material to the glass composition, microcrystalline glass or microcrystalline glass product of the present invention; however, as raw materials and/or equipment for producing glass compositions, microcrystalline glass or microcrystalline glass products, there will be certain impurities or components that are not intentionally added, which will be contained in small amounts or trace amounts in the final glass composition, microcrystalline glass or microcrystalline glass product, and this situation is also within the scope of protection of the patent of this invention.

In some embodiments of the present invention, the crystalline phases in the glass-ceramics and glass-ceramics products contain lithium disilicate and petalite, and/or quartz and quartz solid solutions, which provide high strength for the glass-ceramics and glass-ceramics products of the present invention, and the fracture toughness of the glass-ceramics and glass-ceramics products increases; the drop ball test height and four-point bending strength of the glass-ceramics and glass-ceramics products increase; the haze decreases, and the light transmittance increases. The glass-ceramics of the present invention have excellent chemical strengthening properties, and can also be chemically strengthened to obtain better mechanical strength. Through reasonable component design, the glass-ceramics and glass-ceramics products of the present invention can obtain a suitable grain size, so that the glass-ceramics and glass-ceramics products of the present invention have high strength. The glass-ceramics and glass-ceramics products of the present invention have good crystallinity, so that the glass-ceramics and glass-ceramics products of the present invention have excellent mechanical properties. The crystallinity referred to herein refers to the completeness of crystallization. The arrangement of particles inside a complete crystal is relatively regular, the diffraction lines are strong, sharp and symmetrical, and the half-width of the diffraction peak is close to the width measured by the instrument. Crystals with poor crystallinity have defects such as dislocations, which make the diffraction peak wide and diffuse. The worse the crystallinity, the weaker the diffraction ability and the wider the diffraction peak, until it disappears into the background. In some embodiments, the crystallinity of the microcrystalline glass product or microcrystalline glass is 55% or more, preferably 65% or more, and more preferably 75% or more.

The grain size and type in the glass-ceramics or glass-ceramics products of the present invention will affect the haze and transmittance of the glass-ceramics or glass-ceramics products. The smaller the grains, the higher the transmittance, and the smaller the haze, the higher the transmittance. In some embodiments, the haze of glass-ceramics products or glass-ceramics with a thickness of less than 1 mm is less than 0.2%, preferably less than 0.15%, and more preferably less than 0.12%. In some embodiments, the grain size of the glass-ceramics products or glass-ceramics is less than 35 nm, preferably less than 30 nm, and more preferably less than 25 nm.

In some embodiments, the glass-ceramics or glass-ceramics products of the present invention exhibit high transmittance in the visible light range. In some embodiments, the average light transmittance of the glass-ceramics products or glass-ceramics with a thickness of less than 1 mm at 400 to 800 nm is preferably 89% or more. In some preferred embodiments, the light transmittance of the glass-ceramics products or glass-ceramics with a thickness of less than 1 mm at 550 nm is preferably 91% or more.

The glass composition, glass-ceramics and glass-ceramics products of the present invention can be produced and manufactured by the following methods:

To form a glass composition: Mix the raw materials evenly according to the composition ratio, put the even mixture into a platinum or quartz crucible, and melt it in an electric furnace or gas furnace at a temperature range of 1400-1650°C for 5-24 hours, depending on the melting difficulty of the glass composition. After melting and stirring to make it even, cool it down to an appropriate temperature, cast it into a mold, and slowly cool it.

The glass composition of the present invention can be formed by a well-known method.

The glass composition of the present invention is crystallized by a crystallization process after forming or forming, and crystals are uniformly precipitated inside the glass. The crystallization process can be carried out in one stage, two stages, or three stages. In order to obtain the desired physical properties of the microcrystalline glass, the preferred crystallization process is:

The above-mentioned crystallization treatment is carried out in one stage, and the nucleation process and the crystal growth process can be carried out continuously. That is, the temperature is raised to a specified crystallization treatment temperature, and after reaching the crystallization treatment temperature, the temperature is maintained for a certain period of time, and then the temperature is lowered. The crystallization treatment temperature is preferably 600-750°C, and in order to precipitate the desired crystalline phase, it is more preferably 650-720°C. The holding time at the crystallization treatment temperature is preferably 0-8 hours, and more preferably 1-6 hours.

When the crystallization process is performed in two stages, the nucleation process is performed at the first temperature, and then the crystal growth process is performed at the second temperature. The first temperature is preferably 470 to 600° C., and the second temperature is preferably 600 to 750° C. The holding time at the first temperature is preferably 0 to 24 hours, more preferably 2 to 15 hours. The holding time at the second temperature is preferably 0 to 10 hours, more preferably 0.5 to 6 hours.

When the crystallization process is performed in three stages, the nucleation process is performed at the first temperature, and then the crystal growth process is performed at the second and third temperatures. The first temperature is preferably 470 to 550°C, the second temperature is preferably 570 to 630°C, and the third temperature is preferably 650 to 750°C. The holding time at the first temperature is preferably 0 to 24 hours, more preferably 2 to 15 hours. The holding time at the second temperature is preferably 0 to 10 hours, more preferably 0.5 to 6 hours. The holding time at the third temperature is preferably 0 to 10 hours, more preferably 0.5 to 6 hours.

The above-mentioned holding time of 0 hours means that the temperature starts to drop or rise again within less than 1 minute after reaching the temperature.

In some embodiments, the glass composition or glass-ceramic described herein can be manufactured into a formed body by various processes, including but not limited to a sheet, and the processes include but are not limited to slot drawing, float process, rolling and other processes for forming sheets known in the art. Alternatively, the glass composition or glass-ceramic can be formed by a float process or rolling process known in the art.

The glass composition or glass-ceramics of the present invention can be manufactured into a glass molded body in the form of a sheet by grinding, polishing or the like, but the method for manufacturing the glass molded body is not limited to these methods.

The glass composition or glass-ceramic formed body of the present invention can be formed into various shapes by heat bending or pressing at a certain temperature, but is not limited to these methods.

The glass compositions, glass-ceramics, and glass-ceramics articles described herein can have any reasonably useful thickness.

In addition to improving mechanical properties by crystallization, the microcrystalline glass of the present invention can also obtain higher strength by forming a compressive stress layer, thereby making microcrystalline glass products.

In some embodiments, the glass composition or glass-ceramics can be processed into sheets, and/or shaped (such as punching, hot bending, etc.), polished and/or swept after shaping, and then chemically strengthened through a chemical strengthening process.

The chemical strengthening described in the present invention is an ion exchange method. During the ion exchange process, smaller metal ions in the glass composition or glass-ceramic are replaced or "exchanged" by larger metal ions of the same valence state near the glass composition or glass-ceramic. The replacement of smaller ions with larger ions builds up compressive stress in the glass composition or glass-ceramic, forming a compressive stress layer.

In some embodiments, the metal ions are monovalent alkali metal ions (e.g., Na ⁺ , K ⁺ , Rb ⁺ , Cs ⁺ , etc.), and the ion exchange is performed by immersing the glass composition or glass-ceramic in a salt bath of at least one molten salt containing larger metal ions, which are used to replace smaller metal ions in the glass composition. Alternatively, other monovalent metal ions such as Ag ⁺ , Tl ⁺ , Cu ⁺ , etc. can also be used to exchange monovalent ions. One or more ion exchange processes used to chemically strengthen the glass composition or glass-ceramic may include, but are not limited to, immersing it in a single salt bath, or immersing it in multiple salt baths of the same or different compositions, with washing and/or annealing steps between immersions.

In some embodiments, the glass composition or glass-ceramics can be ion-exchanged by immersing in a salt bath of molten Na salt (such as NaNO ₃ ) at a temperature of about 320°C to 470°C for about 6 to 20 hours, preferably in the temperature range of 360°C to 460°C, and preferably in the time range of 8 to 13 hours. In this embodiment, Na ions replace part of the Li ions in the glass composition or glass-ceramics, thereby forming a surface compression layer and exhibiting high mechanical properties. In some embodiments, the glass composition or glass-ceramics can be ion-exchanged by immersing in a salt bath of molten K salt (such as KNO ₃ ) at a temperature of about 340°C to 450°C for 1 to 24 hours, preferably in the time range of 2 to 10 hours. In some embodiments, the glass composition or glass-ceramics can be ion-exchanged by immersing in a mixed salt bath of molten K salt (such as KNO ₃ ) and molten Na salt (such as NaNO ₃ ) at a temperature of about 340°C to 500°C for 1 to 24 hours, preferably in the time range of 2 to 10 hours.

In some embodiments, there is also an ion implantation method of implanting ions into the surface layer of the glass composition or glass-ceramics, and a heat strengthening method of heating the glass composition or glass-ceramics and then rapidly cooling it.

The various performance indicators of the glass-ceramics and/or glass-ceramics products and/or glass compositions of the present invention are tested by the following methods:

[Haze]

The haze tester EEL57D was used to prepare samples with a thickness of less than 1 mm and the test was carried out according to the standard GB2410-80.

[Grain size]

Using a SEM scanning electron microscope, the microcrystalline glass is surface treated in HF acid, gold is sprayed on the surface of the microcrystalline glass, and the surface is scanned under the SEM scanning electron microscope to determine the size of its grains.

[Light transmittance]

The light transmittances described in this article are all external transmittances, sometimes referred to as transmittance.

The sample was processed to a thickness of less than 1 mm and the opposite surfaces were polished parallel to each other, and the average light transmittance at 400 to 800 nm was measured using a Hitachi U-41000 spectrophotometer.

The sample was processed to a thickness of less than 1 mm and the opposite surfaces were polished parallel to each other, and the light transmittance at 550 nm was measured using a Hitachi U-41000 spectrophotometer.

[Crystallinity]

The XRD diffraction peaks were compared with the database spectrum, and the crystallinity was obtained by calculating the proportion of the crystalline phase diffraction intensity in the overall spectrum intensity, and was internally calibrated by using pure quartz crystals.

[Surface stress] and [Ion exchange layer depth]

The surface stress was measured using a glass surface stress meter SLP-2000.

The depth of the ion exchange layer was measured using a glass surface stress meter SLP-2000.

The calculation was performed under the measurement conditions that the refractive index of the sample was 1.54 and the photoelastic constant was 25.3 [(nm/cm)/Mpa].

[Drop ball test height]

A sample of a microcrystalline glass product of 150mm×57mm×0.7mm is placed on a glass supporting fixture, and a 132g steel ball is dropped from a specified height. The maximum drop ball test height at which the sample can withstand the impact without breaking. Specifically, the test is implemented starting from a drop ball test height of 800mm, and the height is changed in sequence through 850mm, 900mm, 950mm, 1000mm and above without breaking. For the embodiments with a "drop ball test height", microcrystalline glass products are used as test objects. The test data recorded as 1000mm in the embodiment indicates that even if a steel ball is dropped from a height of 1000mm, the microcrystalline glass product will withstand the impact without breaking. The drop ball test height in the present invention is sometimes referred to as the drop ball height.

[Body drop height]

Place a 150mm×57mm×0.7mm microcrystalline glass sample on a glass supporting fixture, and drop a 32g steel ball from a specified height. The maximum drop ball test height that the sample can withstand without breaking is the main body drop ball height. Specifically, the test starts from a drop ball test height of 500mm, and the height is changed in sequence through 550mm, 600mm, 650mm, 700mm and above without breaking. For the embodiments with a "main body drop ball height", microcrystalline glass is used as the test object. The test data recorded as 1000mm in the embodiment indicates that even if a steel ball is dropped from a height of 1000mm, the microcrystalline glass will withstand the impact without breaking.

[Fracture toughness]

The method of directly measuring the size of the indentation extension crack was used. The sample size was 2mm×4mm×20mm. After chamfering, grinding and polishing, the sample preparation was completed. A force of 49N was applied to the sample with a Vickers hardness indenter and maintained for 30s. After the indentation was made, the fracture strength was determined by the three-point bending method.

[Four-point bending strength]

The microcomputer-controlled electronic universal testing machine CMT6502 was used, the sample specification was less than 1mm thick, and the test was carried out according to ASTM C158-2002.

The sample thickness is preferably 0.2 to 1 mm, more preferably 0.3 to 0.9 mm, further preferably 0.5 to 0.8 mm, and further preferably 0.55 mm, 0.6 mm, 0.68 mm, 0.7 mm, or 0.75 mm.

[Vickers hardness]

The value is expressed as the load (N) when a diamond quadrangular pyramid indenter with an angle of 136° between opposite faces presses a pyramid-shaped depression into the test surface, divided by the surface area (mm ² ) calculated from the length of the depression. The test load is 100 (N) and the holding time is 15 (seconds). In the present invention, Vickers hardness is sometimes referred to as simply hardness.

[Coefficient of thermal expansion]

The thermal expansion coefficient (α _20℃-300℃ ) is tested according to the test method of "GB/T7962.16-2010".

[Refractive Index]

The refractive index (n _d ) is tested according to the method of GB/T7962.1-2010.

[|B|value]

Use Minolta CM-700d to test the B value. Use the matching calibration long tube and short tube to perform instrument zero calibration and white plate calibration respectively. After calibration, use the long tube to perform air test to determine the stability and calibration reliability of the instrument (B≤0.05). After the instrument is calibrated, place the product on the zero long tube for testing.

The |B| value is the absolute value of the B value.

[Drop resistance]

The drop resistance test was carried out using the directional drop tester WH-2101. By loading glass products of the same specifications on 2D microcrystalline glass products (each piece weighs 20g, and 2 pieces are loaded), laying 60-80 mesh sandpaper on the base, and letting the sample fall freely from a specified height, the sample directly hits the sandpaper, and the height of the impact that can be withstood without breaking is the drop resistance. Specifically, the test is implemented from a height of 600mm, and the height is changed in sequence through 700mm, 800mm, 900mm, 1000mm and above without breaking. For the embodiments with "drop resistance", microcrystalline glass products are used as test objects. The test data recorded as 2000mm in the embodiment indicates that even if the microcrystalline glass products with load from a height of 2000mm do not break and withstand the impact, the maximum experimental height of the drop tester WH-2101 is 2000mm.

The microcrystalline glass product of the present invention has the following properties:

1) In some embodiments, the four-point bending strength of the glass-ceramic product is 680 MPa or more, preferably 700 MPa or more, and more preferably 720 MPa or more.

2) In some embodiments, the depth of the ion exchange layer of the microcrystalline glass product is greater than 85 μm, preferably greater than 100 μm, and more preferably greater than 110 μm.

3) In some embodiments, the surface stress of the microcrystalline glass product is greater than 150 MPa, preferably greater than 180 MPa, and more preferably greater than 200 MPa.

4) In some embodiments, the drop ball test height of the glass-ceramic product is greater than 1500 mm, preferably greater than 1600 mm, and more preferably greater than 1700 mm.

5) In some embodiments, the fracture toughness of the glass-ceramic product is greater than 1 MPa·m ^1/2 , preferably greater than 1.1 MPa·m ^1/2 , and more preferably greater than 1.2 MPa·m ^1/2 .

6) In some embodiments, the Vickers hardness of the microcrystalline glass product is 750 kgf/mm ² or more, preferably 780 kgf/mm ² or more, and more preferably 800 kgf/mm ² or more.

7) In some embodiments, the crystallinity of the glass-ceramic product is 55% or more, preferably 65% or more, and more preferably 75% or more.

8) In some embodiments, the grain size of the microcrystalline glass product is less than 35 nm, preferably less than 30 nm, and more preferably less than 25 nm.

9) In some embodiments, the haze of the microcrystalline glass product with a thickness of 1 mm or less is 0.2% or less, preferably 0.15% or less, and more preferably 0.12% or less. The thickness is preferably 0.2-1 mm, more preferably 0.3-0.9 mm, further preferably 0.5-0.8 mm, and further preferably 0.55 mm, 0.6 mm, 0.68 mm, 0.7 mm, or 0.75 mm.

10) In some embodiments, the average transmittance of the microcrystalline glass product with a thickness of 1 mm or less at a wavelength of 400 to 800 nm is 87% or more, preferably 88% or more, and more preferably 89% or more. The thickness is preferably 0.2 to 1 mm, more preferably 0.3 to 0.9 mm, further preferably 0.5 to 0.8 mm, and further preferably 0.55 mm, 0.6 mm, 0.68 mm, 0.7 mm, or 0.75 mm.

11) In some embodiments, the transmittance of the glass-ceramic product with a thickness of 1 mm or less at a wavelength of 550 nm is 88% or more, preferably 90% or more, and more preferably 91% or more. The thickness is preferably 0.2 to 1 mm, more preferably 0.3 to 0.9 mm, further preferably 0.5 to 0.8 mm, and further preferably 0.55 mm, 0.6 mm, 0.68 mm, 0.7 mm, or 0.75 mm.

12) In some embodiments, for a glass-ceramic product having a thickness of less than 1 mm, the average optical |B| value at 400-800 nm is less than 0.8, preferably less than 0.75, and more preferably less than 0.7. The thickness is preferably 0.2-1 mm, more preferably 0.3-0.9 mm, further preferably 0.5-0.8 mm, and further preferably 0.55 mm, 0.6 mm, 0.68 mm, 0.7 mm, or 0.75 mm.

13) In some embodiments, the drop resistance of a glass-ceramic product with a thickness of less than 1 mm is 1700 mm or more, preferably 1800 mm or more, and more preferably 2000 mm or more. The thickness is preferably 0.2 to 1 mm, more preferably 0.3 to 0.9 mm, more preferably 0.5 to 0.8 mm, and even more preferably 0.55 mm, 0.6 mm, 0.68 mm, 0.7 mm, or 0.75 mm.

The microcrystalline glass of the present invention has the following properties:

1) In some embodiments, the crystallinity of the glass-ceramics is 55% or more, preferably 65% or more, and more preferably 75% or more.

2) In some embodiments, the grain size of the microcrystalline glass is less than 35 nm, preferably less than 30 nm, and preferably less than 25 nm.

3) In some embodiments, the haze of the microcrystalline glass with a thickness of 1 mm or less is 0.2% or less, preferably 0.15% or less, and more preferably 0.12% or less. The thickness is preferably 0.2-1 mm, more preferably 0.3-0.9 mm, further preferably 0.5-0.8 mm, and further preferably 0.55 mm, 0.6 mm, 0.68 mm, 0.7 mm, or 0.75 mm.

4) In some embodiments, the average transmittance of the glass-ceramics with a thickness of less than 1 mm at a wavelength of 400 to 800 nm is 87% or more, preferably 88% or more, and more preferably 89% or more. The thickness is preferably 0.2 to 1 mm, more preferably 0.3 to 0.9 mm, further preferably 0.5 to 0.8 mm, and further preferably 0.55 mm, 0.6 mm, 0.68 mm, 0.7 mm, or 0.75 mm.

5) In some embodiments, the transmittance of the microcrystalline glass with a thickness of 1 mm or less at a wavelength of 550 nm is 88% or more, preferably 90% or more, and more preferably 91% or more. The thickness is preferably 0.2 to 1 mm, more preferably 0.3 to 0.9 mm, further preferably 0.5 to 0.8 mm, and further preferably 0.55 mm, 0.6 mm, 0.68 mm, 0.7 mm, or 0.75 mm.

6) In some embodiments, for a glass-ceramic product having a thickness of less than 1 mm, the average optical |B| value at 400-800 nm is less than 0.8, preferably less than 0.75, and more preferably less than 0.7. The thickness is preferably 0.2-1 mm, more preferably 0.3-0.9 mm, further preferably 0.5-0.8 mm, and further preferably 0.55 mm, 0.6 mm, 0.68 mm, 0.7 mm, or 0.75 mm.

7) In some embodiments, the ball drop height of the microcrystalline glass body is greater than 1800 mm, preferably greater than 1900 mm, and more preferably greater than 2000 mm.

8) In some embodiments, the Vickers hardness of the glass-ceramics is 680 kgf/mm ² or more, preferably 700 kgf/mm ² or more, and more preferably 710 kgf/mm ² or more.

9) In some embodiments, the thermal expansion coefficient (α _20°C-120°C ) of the glass-ceramics is 60×10 ^-7 /K to 90×10 ^-7 /K.

10) In some embodiments, the refractive index (n _d ) of the glass-ceramics is 1.5250 to 1.5450.

The glass composition of the present invention has the following properties:

1) In some embodiments, the thermal expansion coefficient (α _20°C-120°C ) of the glass composition is 55×10 ^-7 /K to 65×10 ^-7 /K.

2) In some embodiments, the glass composition has a refractive index (n _d ) of 1.5100 to 1.5300.

The microcrystalline glass, microcrystalline glass products and glass compositions of the present invention can be widely made into glass cover plates or glass components due to the above-mentioned excellent properties; at the same time, the microcrystalline glass, microcrystalline glass products and glass compositions of the present invention are applied to electronic devices or display devices, such as mobile phones, watches, computers, touch screens, etc., for manufacturing protective glass for mobile phones, smart phones, tablet computers, laptops, PDAs, televisions, personal computers, MTA machines or industrial displays, or for manufacturing touch screens, protective windows, car windows, train windows, aviation machinery windows, touch screen protective glass, or for manufacturing hard disk substrates or solar cell substrates, or for manufacturing white household appliances, such as for manufacturing refrigerator parts or kitchen utensils.

Example

In order to further clearly illustrate and describe the technical solution of the present invention, the following non-limiting examples are provided. The present invention embodiments have been tried to ensure the accuracy of the values (such as quantity, temperature, etc.), but some errors and deviations must be taken into account. The composition itself is given in weight % based on the oxide and has been standardized to 100%.

<Glass Composition Example>

In this example, the above-mentioned method for producing a glass composition is used to obtain a glass composition having the composition shown in Tables 1 and 2. In addition, the properties of each glass composition are measured by the test method described in the present invention, and the measurement results are shown in Tables 1 and 2.

Table 1.

Table 2.

<Glass-ceramic Example>

This embodiment adopts the above-mentioned method for manufacturing microcrystalline glass to obtain microcrystalline glass having the composition shown in Tables 3 and 4. In addition, the properties of each microcrystalline glass are measured by the testing method described in the present invention, and the measurement results are shown in Tables 3 and 4. The sample test thickness of the microcrystalline glass in the embodiment is 0.7 mm.

Table 3.

Table 4.

<Glass-ceramic product example>

This embodiment adopts the above-mentioned method for manufacturing microcrystalline glass products to obtain microcrystalline glass products having the compositions shown in Tables 5 and 6. In addition, the properties of each microcrystalline glass product are measured by the testing method described in the present invention, and the measurement results are shown in Tables 5 and 6. The sample test thickness of the microcrystalline glass product in the embodiment is 0.7 mm.

Table 5.

Table 6.

Claims (41)

1. A glass ceramic product is characterized by comprising the following components in mole percent ：SiO₂：65～75％;Al₂O₃：1～8％;Li₂O：14～25％;P₂O₅+ZrO₂：0.5～6％.

2. The glass-ceramic article according to claim 1, wherein the composition, expressed in mole percent, further comprises: znO+MgO:0 to 4 percent; and/or Na ₂ O:0 to 3.5 percent; and/or B ₂O₃: 0 to 3 percent; and/or K ₂ O:0 to 3 percent; and/or SrO:0 to 3 percent; and/or BaO:0 to 3 percent; and/or CaO:0 to 3 percent; and/or TiO ₂: 0 to 3 percent; and/or Y ₂O₃: 0 to 3 percent; and/or clarifying agent: 0 to 1 percent.

3. A glass-ceramic article characterized by its composition, expressed in mole percent, as specified by SiO₂：65～75％;Al₂O₃：1～8％;Li₂O：14～25％;P₂O₅+ZrO₂：0.5～6％;ZnO+MgO：0～4％;Na₂O：0～3.5％;B₂O₃：0～3％;K₂O：0～3％;SrO：0～3％;BaO：0～3％;CaO：0～3％;TiO₂：0～3％;Y₂O₃：0～3％; fining agent: 0-1%.

4. The glass-ceramic product is characterized by comprising SiO ₂、Al₂O₃ and Li ₂ O as essential components, wherein the crystal phase of the glass-ceramic product contains lithium silicate, and the shatter resistance of the glass-ceramic product is 1700mm or more.

5. The glass-ceramic article according to claim 4, wherein the composition comprises, in mole percent: siO ₂: 65-75%; and/or Al ₂O₃: 1 to 8 percent; and/or Li ₂ O: 14-25%; and/or P ₂O₅+ZrO₂: 0.5 to 6 percent; and/or zno+mgo:0 to 4 percent; and/or Na ₂ O:0 to 3.5 percent; and/or B ₂O₃: 0 to 3 percent; and/or K ₂ O:0 to 3 percent; and/or SrO:0 to 3 percent; and/or BaO:0 to 3 percent; and/or CaO:0 to 3 percent; and/or TiO ₂: 0 to 3 percent; and/or Y ₂O₃: 0 to 3 percent; and/or clarifying agent: 0 to 1 percent.

6. The glass-ceramic article according to any one of claims 1 to 5, wherein the components, expressed in mole percent, satisfy one or more of the following 5 conditions:

1) (Li ₂O+ZrO₂)/(ZnO+MgO) is 10 or more, preferably (Li ₂O+ZrO₂)/(ZnO+MgO) is 12 to 45, more preferably (Li ₂O+ZrO₂)/(ZnO+MgO) is 13 to 40, still more preferably (Li ₂O+ZrO₂)/(ZnO+MgO) is 15 to 35, still more preferably (Li ₂O+ZrO₂)/(ZnO+MgO) is 20 to 30, still more preferably (Li ₂O+ZrO₂)/(ZnO+MgO) is 24 to 29;

2) (B ₂O₃+Na₂O+ZrO₂)/(Al₂O₃ +MgO) is 0.05 to 1.5, preferably (B ₂O₃+Na₂O+ZrO₂)/(Al₂O₃ +MgO) is 0.1 to 1, more preferably (B ₂O₃+Na₂O+ZrO₂)/(Al₂O₃ +MgO) is 0.15 to 0.8, still more preferably (B ₂O₃+Na₂O+ZrO₂)/(Al₂O₃ +MgO) is 0.2 to 0.7, still more preferably (B ₂O₃+Na₂O+ZrO₂)/(Al₂O₃ +MgO) is 0.2 to 0.6, still more preferably (B ₂O₃+Na₂O+ZrO₂)/(Al₂O₃ +MgO) is 0.25 to 0.5;

3) (SiO ₂+Li₂O)/(Al₂O₃ +ZnO+MgO) is 5 to 40, preferably (SiO ₂+Li₂O)/(Al₂O₃ +ZnO+MgO) is 8 to 30, more preferably (SiO ₂+Li₂O)/(Al₂O₃ +ZnO+MgO) is 10 to 25, still more preferably (SiO ₂+Li₂O)/(Al₂O₃ +ZnO+MgO) is 11 to 20, still more preferably (SiO ₂+Li₂O)/(Al₂O₃ +ZnO+MgO) is 13 to 20, still more preferably (SiO ₂+Li₂O)/(Al₂O₃ +ZnO+MgO) is 16 to 19.6;

4)(SiO₂+Al₂O₃+Li₂O+Na₂O+ZrO₂)/(P₂O₅+MgO) 30 to 90, preferably (SiO₂+Al₂O₃+Li₂O+Na₂O+ZrO₂)/(P₂O₅+MgO) to 80, more preferably (SiO₂+Al₂O₃+Li₂O+Na₂O+ZrO₂)/(P₂O₅+MgO) to 38 to 75, further preferably (SiO₂+Al₂O₃+Li₂O+Na₂O+ZrO₂)/(P₂O₅+MgO) to 40 to 70, further preferably (SiO₂+Al₂O₃+Li₂O+Na₂O+ZrO₂)/(P₂O₅+MgO) to 50 to 69, further preferably (SiO₂+Al₂O₃+Li₂O+Na₂O+ZrO₂)/(P₂O₅+MgO) to 60 to 68;

5) (SiO ₂+Al₂O₃)/(P₂O₅+ZrO₂) is 12 to 75, preferably (SiO ₂+Al₂O₃)/(P₂O₅+ZrO₂) is 15 to 70, more preferably (SiO ₂+Al₂O₃)/(P₂O₅+ZrO₂) is 17 to 65, still more preferably (SiO ₂+Al₂O₃)/(P₂O₅+ZrO₂) is 20 to 60, still more preferably (SiO ₂+Al₂O₃)/(P₂O₅+ZrO₂) is 30 to 50, still more preferably (SiO ₂+Al₂O₃)/(P₂O₅+ZrO₂) is 35 to 40.

7. The glass-ceramic article according to any one of claims 1 to 5, wherein the components are expressed in mole percent, wherein: siO ₂: 67-73%, preferably SiO ₂: 68-72%; and/or Al ₂O₃: 2 to 6.5%, preferably Al ₂O₃: 3 to 6 percent; And/or Li ₂ O:15.5 to 24%, preferably Li ₂ O:17 to 23.5 percent; and/or zno+mgo:0.1 to 4%, preferably ZnO+MgO:0.2 to 3%, more preferably zno+mgo:0.5 to 2 percent; and/or P ₂O₅+ZrO₂: 1-4%, preferably P ₂O₅+ZrO₂: 1.2 to 3 percent; And/or Na ₂ O:0.5 to 3%, preferably Na ₂ O:0.5 to 2.5 percent; and/or B ₂O₃: 0.5 to 2.5%, preferably B ₂O₃: 0.5 to 2 percent; and/or K ₂ O:0 to 2%, preferably K ₂ O:0 to 1.5 percent; and/or SrO: 0-2%, preferably SrO:0 to 1 percent; and/or BaO: 0-2%, preferably BaO:0 to 1 percent; and/or CaO:0 to 2%, preferably CaO:0 to 1 percent; and/or TiO ₂: 0 to 2%, preferably TiO ₂: 0 to 1 percent; And/or Y ₂O₃: 0 to 2%, preferably Y ₂O₃: 0 to 1 percent; and/or clarifying agent: 0 to 0.5%, preferably a clarifying agent: 0 to 0.2 percent.

8. The glass-ceramic article according to any one of claims 1 to 5, wherein the components are expressed in mole percent, wherein: znO:0 to 2%, preferably ZnO:0 to 1.5%, more preferably ZnO:0 to 1 percent; and/or MgO:0 to 4%, preferably MgO:0 to 3%, more preferably MgO:0 to 1.5 percent; and/or P ₂O₅: 0-3%, preferably P ₂O₅: 0.2 to 2%, more preferably P ₂O₅: 0.4 to 1.5%, more preferably P ₂O₅: 0.5 to 1 percent; and/or ZrO ₂: 0 to 4%, preferably ZrO ₂: 0.2 to 3.5%, more preferably ZrO ₂: 0.5 to 3%, more preferably ZrO ₂: 0.7 to 2.5 percent.

9. The glass-ceramic article according to any one of claims 1 to 5, wherein the glass-ceramic article comprises lithium silicate in a crystalline phase; and/or quartz and a quartz solid solution; and/or petalite, preferably the crystalline phase in the glass-ceramic product contains lithium disilicate and petalite, the total content of the lithium disilicate and the petalite has a higher weight percentage than other crystalline phases, more preferably the total content of the lithium disilicate and the petalite crystalline phase accounts for 50 to 80 weight percent of the glass-ceramic product, still more preferably the total content of the lithium disilicate and the petalite crystalline phase accounts for 55 to 75 weight percent of the glass-ceramic product, still more preferably the total content of the lithium disilicate and the petalite crystalline phase accounts for 55 to 70 weight percent of the glass-ceramic product.

10. The glass-ceramic article according to any one of claims 1 to 5, wherein the lithium disilicate crystalline phase comprises 15 to 40% by weight of the glass-ceramic article, preferably the lithium disilicate crystalline phase comprises 20 to 35% by weight of the glass-ceramic article, more preferably the lithium disilicate crystalline phase comprises 25 to 35% by weight of the glass-ceramic article; and/or the petalite crystal phase accounts for 30-55% of the weight of the glass ceramic product, preferably the petalite crystal phase accounts for 35-55% of the weight of the glass ceramic product, and more preferably the petalite crystal phase accounts for 35-50% of the weight of the glass ceramic product; and/or the quartz and quartz solid solution crystalline phase accounts for 5-25% of the weight of the glass ceramics, preferably Dan Yingji quartz solid solution crystalline phase accounts for 7-20% of the weight of the glass ceramics; and/or the lithium silicate crystalline phase accounts for 0-10% of the weight of the glass-ceramic product, preferably the lithium silicate crystalline phase accounts for 0-7% of the weight of the glass-ceramic product, and more preferably the lithium silicate crystalline phase accounts for 0-5% of the weight of the glass-ceramic product.

11. The glass-ceramic article according to any one of claims 1 to 5, wherein the glass-ceramic article has a four-point bending strength of 680MPa or more, preferably 700MPa or more, more preferably 720MPa or more; and/or the ion exchange layer depth of the glass-ceramic product is 85 μm or more, preferably 100 μm or more, more preferably 110 μm or more; and/or the surface stress of the glass-ceramic product is 150MPa or more, preferably 180MPa or more, more preferably 200MPa or more; and/or the glass-ceramic product has a falling ball test height of 1500mm or more, preferably 1600mm or more, more preferably 1700mm or more; and/or the glass ceramic product has a fracture toughness of 1 MPa.m ^1/2 or more, preferably 1.1 MPa.m ^1/2 or more, more preferably 1.2 MPa.m ^1/2 or more; and/or the glass ceramic product has a vickers hardness of 750kgf/mm ² or more, preferably 780kgf/mm ² or more, more preferably 800kgf/mm ² or more; and/or the crystallinity of the glass-ceramic product is 55% or more, preferably 65% or more, more preferably 75% or more; and/or the crystallite size of the glass-ceramic product is 35nm or less, preferably 30nm or less, more preferably 25nm or less.

12. The glass-ceramic product according to any one of claims 1 to 5, wherein the glass-ceramic product having a thickness of 1mm or less has a haze of 0.2% or less, preferably 0.15% or less, more preferably 0.12% or less; and/or a glass-ceramic product having a thickness of 1mm or less, wherein the average transmittance at a wavelength of 400 to 800nm is 87% or more, preferably 88% or more, and more preferably 89% or more; and/or a glass ceramic product having a thickness of 1mm or less, and a transmittance at a wavelength of 550nm of 88% or more, preferably 90% or more, more preferably 91% or more; and/or a glass-ceramic product having a thickness of 1mm or less, and an average light-B-value of 400 to 800nm of 0.8 or less, preferably 0.75 or less, more preferably 0.7 or less; and/or the shatter resistance of the glass ceramic product having a thickness of 1mm or less is 1700mm or more, preferably 1800mm or more, more preferably 2000mm or more.

13. The glass-ceramic article according to claim 12, wherein the glass-ceramic article has a thickness of 0.2 to 1mm, preferably 0.3 to 0.9mm, more preferably 0.5 to 0.8mm, even more preferably 0.55mm or 0.6mm or 0.68mm or 0.7mm or 0.75mm.

14. The microcrystalline glass is characterized by comprising the following components in percentage by mole ：SiO₂：65～75％;Al₂O₃：1～8％;Li₂O：14～25％;P₂O₅+ZrO₂：0.5～6％.

15. The glass-ceramic according to claim 14, further comprising, in mole percent: znO+MgO:0 to 4 percent; and/or Na ₂ O:0 to 3.5 percent; and/or B ₂O₃: 0 to 3 percent; and/or K ₂ O:0 to 3 percent; and/or SrO:0 to 3 percent; and/or BaO:0 to 3 percent; and/or CaO:0 to 3 percent; and/or TiO ₂: 0 to 3 percent; and/or Y ₂O₃: 0 to 3 percent; and/or clarifying agent: 0 to 1 percent.

16. The microcrystalline glass is characterized by comprising the following components in percentage by mole: 0-1%.

17. A glass-ceramic comprising SiO ₂、Al₂O₃、Li₂ O as an essential component, wherein the crystal phase of the glass-ceramic comprises lithium disilicate and petalite, the total content of the lithium disilicate and the petalite is higher than that of other crystal phases by weight, and the haze of the glass-ceramic having a thickness of 1mm or less is 0.2% or less.

18. The glass-ceramic according to claim 17, wherein the composition comprises, in mole percent: siO ₂: 65-75%; and/or Al ₂O₃: 1 to 8 percent; and/or Li ₂ O: 14-25%; and/or P ₂O₅+ZrO₂: 0.5 to 6 percent; and/or zno+mgo:0 to 4 percent; and/or Na ₂ O:0 to 3.5 percent; and/or B ₂O₃: 0 to 3 percent; and/or K ₂ O:0 to 3 percent; and/or SrO:0 to 3 percent; and/or BaO:0 to 3 percent; and/or CaO:0 to 3 percent; and/or TiO ₂: 0 to 3 percent; and/or Y ₂O₃: 0 to 3 percent; and/or clarifying agent: 0 to 1 percent.

19. A glass-ceramic according to any one of claims 14 to 18, wherein the composition, expressed in mole percent, satisfies one or more of the following 5 conditions:

1) (Li ₂O+ZrO₂)/(ZnO+MgO) is 10 or more, preferably (Li ₂O+ZrO₂)/(ZnO+MgO) is 12 to 45, more preferably (Li ₂O+ZrO₂)/(ZnO+MgO) is 13 to 40, still more preferably (Li ₂O+ZrO₂)/(ZnO+MgO) is 15 to 35, still more preferably (Li ₂O+ZrO₂)/(ZnO+MgO) is 20 to 30, still more preferably (Li ₂O+ZrO₂)/(ZnO+MgO) is 24 to 29;

2) (B ₂O₃+Na₂O+ZrO₂)/(Al₂O₃ +MgO) is 0.05 to 1.5, preferably (B ₂O₃+Na₂O+ZrO₂)/(Al₂O₃ +MgO) is 0.1 to 1, more preferably (B ₂O₃+Na₂O+ZrO₂)/(Al₂O₃ +MgO) is 0.15 to 0.8, still more preferably (B ₂O₃+Na₂O+ZrO₂)/(Al₂O₃ +MgO) is 0.2 to 0.7, still more preferably (B ₂O₃+Na₂O+ZrO₂)/(Al₂O₃ +MgO) is 0.2 to 0.6, still more preferably (B ₂O₃+Na₂O+ZrO₂)/(Al₂O₃ +MgO) is 0.25 to 0.5;

3) (SiO ₂+Li₂O)/(Al₂O₃ +ZnO+MgO) is 5 to 40, preferably (SiO ₂+Li₂O)/(Al₂O₃ +ZnO+MgO) is 8 to 30, more preferably (SiO ₂+Li₂O)/(Al₂O₃ +ZnO+MgO) is 10 to 25, still more preferably (SiO ₂+Li₂O)/(Al₂O₃ +ZnO+MgO) is 11 to 20, still more preferably (SiO ₂+Li₂O)/(Al₂O₃ +ZnO+MgO) is 13 to 20, still more preferably (SiO ₂+Li₂O)/(Al₂O₃ +ZnO+MgO) is 16 to 19.6;

4)(SiO₂+Al₂O₃+Li₂O+Na₂O+ZrO₂)/(P₂O₅+MgO) 30 to 90, preferably (SiO₂+Al₂O₃+Li₂O+Na₂O+ZrO₂)/(P₂O₅+MgO) to 80, more preferably (SiO₂+Al₂O₃+Li₂O+Na₂O+ZrO₂)/(P₂O₅+MgO) to 38 to 75, further preferably (SiO₂+Al₂O₃+Li₂O+Na₂O+ZrO₂)/(P₂O₅+MgO) to 40 to 70, further preferably (SiO₂+Al₂O₃+Li₂O+Na₂O+ZrO₂)/(P₂O₅+MgO) to 50 to 69, further preferably (SiO₂+Al₂O₃+Li₂O+Na₂O+ZrO₂)/(P₂O₅+MgO) to 60 to 68;

5) (SiO ₂+Al₂O₃)/(P₂O₅+ZrO₂) is 12 to 75, preferably (SiO ₂+Al₂O₃)/(P₂O₅+ZrO₂) is 15 to 70, more preferably (SiO ₂+Al₂O₃)/(P₂O₅+ZrO₂) is 17 to 65, still more preferably (SiO ₂+Al₂O₃)/(P₂O₅+ZrO₂) is 20 to 60, still more preferably (SiO ₂+Al₂O₃)/(P₂O₅+ZrO₂) is 30 to 50, still more preferably (SiO ₂+Al₂O₃)/(P₂O₅+ZrO₂) is 35 to 40.

20. The glass-ceramic according to any one of claims 14 to 18, wherein the components are expressed in mole percent, wherein: siO ₂: 67-73%, preferably SiO ₂: 68-72%; and/or Al ₂O₃: 2 to 6.5%, preferably Al ₂O₃: 3 to 6 percent; And/or Li ₂ O:15.5 to 24%, preferably Li ₂ O:17 to 23.5 percent; and/or zno+mgo:0.1 to 4%, preferably ZnO+MgO:0.2 to 3%, more preferably zno+mgo:0.5 to 2 percent; and/or P ₂O₅+ZrO₂: 1-4%, preferably P ₂O₅+ZrO₂: 1.2 to 3 percent; And/or Na ₂ O:0.5 to 3%, preferably Na ₂ O:0.5 to 2.5 percent; and/or B ₂O₃: 0.5 to 2.5%, preferably B ₂O₃: 0.5 to 2 percent; and/or K ₂ O:0 to 2%, preferably K ₂ O:0 to 1.5 percent; and/or SrO: 0-2%, preferably SrO:0 to 1 percent; and/or BaO: 0-2%, preferably BaO:0 to 1 percent; and/or CaO:0 to 2%, preferably CaO:0 to 1 percent; and/or TiO ₂: 0 to 2%, preferably TiO ₂: 0 to 1 percent; And/or Y ₂O₃: 0 to 2%, preferably Y ₂O₃: 0 to 1 percent; and/or clarifying agent: 0 to 0.5%, preferably a clarifying agent: 0 to 0.2 percent.

21. The glass-ceramic according to any one of claims 14 to 18, wherein the components are expressed in mole percent, wherein: znO:0 to 2%, preferably ZnO:0 to 1.5%, more preferably ZnO:0 to 1 percent; and/or MgO:0 to 4%, preferably MgO:0 to 3%, more preferably MgO:0 to 1.5 percent; and/or P ₂O₅: 0-3%, preferably P ₂O₅: 0.2 to 2%, more preferably P ₂O₅: 0.4 to 1.5%, more preferably P ₂O₅: 0.5 to 1 percent; and/or ZrO ₂: 0 to 4%, preferably ZrO ₂: 0.2 to 3.5%, more preferably ZrO ₂: 0.5 to 3%, more preferably ZrO ₂: 0.7 to 2.5 percent.

22. The glass-ceramic according to any one of claims 14 to 18, wherein the glass-ceramic comprises lithium silicate in a crystalline phase; and/or quartz and a quartz solid solution; and/or petalite, preferably, the crystalline phase in the glass-ceramic contains lithium disilicate and petalite, the total content of the lithium disilicate and the petalite has a higher weight percentage than other crystalline phases, more preferably, the total content of the lithium disilicate and the petalite crystalline phase accounts for 50 to 80 weight percent of the glass-ceramic, still more preferably, the total content of the lithium disilicate and the petalite crystalline phase accounts for 55 to 75 weight percent of the glass-ceramic, still more preferably, the total content of the lithium disilicate and the petalite crystalline phase accounts for 55 to 70 weight percent of the glass-ceramic.

23. The glass-ceramic according to any one of claims 14 to 18, wherein the lithium disilicate crystalline phase comprises 15 to 40% by weight of the glass-ceramic, preferably the lithium disilicate crystalline phase comprises 20 to 35% by weight of the glass-ceramic, more preferably the lithium disilicate crystalline phase comprises 25 to 35% by weight of the glass-ceramic; and/or the petalite crystal phase accounts for 30-55% of the glass ceramics in weight, preferably the petalite crystal phase accounts for 35-55% of the glass ceramics in weight, more preferably the petalite crystal phase accounts for 35-50% of the glass ceramics in weight; and/or the quartz and quartz solid solution crystalline phase accounts for 5-25% of the weight of the glass ceramics, preferably Dan Yingji quartz solid solution crystalline phase accounts for 7-20% of the weight of the glass ceramics; and/or the lithium silicate crystalline phase accounts for 0-10% of the glass ceramics by weight, preferably the lithium silicate crystalline phase accounts for 0-7% of the glass ceramics by weight, and more preferably the lithium silicate crystalline phase accounts for 0-5% of the glass ceramics by weight.

24. The glass-ceramic according to any one of claims 14 to 18, wherein the glass-ceramic has a crystallinity of 55% or more, preferably 65% or more, more preferably 75% or more; and/or the crystallite size of the glass ceramics is below 35nm, preferably below 30nm, preferably below 25 nm; and/or the glass ceramic body has a ball height of 1800mm or more, preferably 1900mm or more, more preferably 2000mm or more; and/or the glass ceramic has a vickers hardness of 680kgf/mm ² or more, preferably 700kgf/mm ² or more, more preferably 710kgf/mm ² or more; and/or the thermal expansion coefficient of the glass ceramics is 60 multiplied by 10 ^-7/K～90×10^-7/K; and/or the refractive index of the glass ceramics is 1.5250-1.5450.

25. The glass-ceramic according to any one of claims 14 to 18, wherein the glass-ceramic has a haze of 0.2% or less, preferably 0.15% or less, more preferably 0.12% or less, with a thickness of 1mm or less; and/or glass ceramics having a thickness of 1mm or less, and an average transmittance at a wavelength of 400 to 800nm of 87% or more, preferably 88% or more, more preferably 89% or more; and/or glass ceramics having a thickness of 1mm or less, and a transmittance at a wavelength of 550nm of 88% or more, preferably 90% or more, more preferably 91% or more; and/or glass ceramics having a thickness of 1mm or less, and an average light-B-value of 400 to 800nm of 0.8 or less, preferably 0.75 or less, more preferably 0.7 or less.

26. The glass-ceramic according to claim 25, wherein the thickness of the glass-ceramic is 0.2-1 mm, preferably 0.3-0.9 mm, more preferably 0.5-0.8 mm, even more preferably 0.55mm or 0.6mm or 0.68mm or 0.7mm or 0.75mm.

27. Glass cover plate, characterized in that it is made of a glass-ceramic product according to any one of claims 1 to 13 and/or of a glass-ceramic according to any one of claims 14 to 26.

28. Glass components, characterized in that they are made of a glass-ceramic product according to any one of claims 1 to 13 and/or of a glass-ceramic according to any one of claims 14 to 26.

29. Display device, characterized in that it comprises a glass-ceramic product according to any one of claims 1 to 13 and/or a glass-ceramic according to any one of claims 14 to 26 and/or a glass cover plate according to claim 27 and/or a glass component according to claim 28.

30. Electronic equipment comprising a glass-ceramic product according to any one of claims 1 to 13 and/or comprising a glass-ceramic according to any one of claims 14 to 26 and/or comprising a glass cover plate according to claim 27 and/or comprising a glass component according to claim 28.

31. The method of manufacturing a glass ceramic product according to any one of claims 1 to 13, characterized in that the method comprises the steps of: forming a glass composition, forming microcrystalline glass from the glass composition through a crystallization process, and forming a microcrystalline glass product from the microcrystalline glass through a chemical strengthening process.

32. The method for producing a glass-ceramic product according to claim 31, wherein the glass composition is produced into a glass-ceramic molded body, and then the glass-ceramic molded body is crystallized to form a glass-ceramic product, and then the glass-ceramic is chemically strengthened to form a glass-ceramic product, or the glass-ceramic is produced into a glass-ceramic molded body, and then the glass-ceramic molded body is chemically strengthened to form a glass-ceramic product.

33. The method of manufacturing a glass-ceramic article according to claim 31, wherein the crystallization process comprises the steps of: heating to a prescribed crystallization temperature, maintaining the temperature for a certain period of time after reaching the crystallization temperature, and then cooling, wherein the crystallization temperature is 600-750 ℃, preferably 650-720 ℃, and the maintaining time at the crystallization temperature is 0-8 hours, preferably 1-6 hours.

34. The method of manufacturing a glass-ceramic article according to claim 31, wherein the crystallization process comprises the steps of: the nucleation process is carried out at a1 st temperature, followed by the crystal growth process at a2 nd temperature, the 1 st temperature being 470 to 600 ℃, the holding time at the 1 st temperature being 0 to 24 hours, preferably 2 to 15 hours, the 2 nd temperature being 600 to 750 ℃, the holding time at the 2 nd temperature being 0 to 10 hours, preferably 0.5 to 6 hours.

35. The method of manufacturing a glass-ceramic article according to claim 31, wherein the crystallization process comprises the steps of: the nucleation process is performed at a1 st temperature, and then the crystal growth process is performed at a2 nd temperature and a 3 rd temperature, wherein the 1 st temperature is 470 to 550 ℃, the holding time at the 1 st temperature is 0 to 24 hours, preferably 2 to 15 hours, the 2 nd temperature is 570 to 630 ℃, the holding time at the 2 nd temperature is 0 to 10 hours, preferably 0.5 to 6 hours, the 3 rd temperature is 650 to 750 ℃, and the holding time at the 3 rd temperature is 0 to 10 hours, preferably 0.5 to 6 hours.

36. The method of manufacturing a glass-ceramic article according to claim 31, wherein the chemical strengthening process comprises: the glass ceramics are immersed in the salt bath of molten Na salt at the temperature of 320 ℃ to 470 ℃ for 6 to 20 hours, the preferable temperature range is 360 ℃ to 460 ℃, and the preferable time range is 8 to 13 hours; and/or the glass ceramics are immersed in a salt bath of molten K salt at the temperature of 340-450 ℃ for 1-24 hours, preferably for 2-10 hours; and/or the glass ceramics are immersed in a salt bath of mixed salt of molten K salt and molten Na salt at the temperature of 340-500 ℃ for 1-24 hours, and the preferable time range is 2-10 hours.

37. The method for producing a glass ceramic according to any one of claims 14 to 26, comprising the steps of: forming a glass composition, and forming microcrystalline glass on the glass composition through a crystallization process.

38. The method for producing a glass ceramic according to claim 37, wherein the glass composition is produced into a glass molded body, and then the glass molded body is crystallized to form a glass ceramic.

39. The method for producing glass ceramics according to claim 37, wherein the crystallization process comprises the steps of: heating to a prescribed crystallization temperature, maintaining the temperature for a certain period of time after reaching the crystallization temperature, and then cooling, wherein the crystallization temperature is 600-750 ℃, preferably 650-720 ℃, and the maintaining time at the crystallization temperature is 0-8 hours, preferably 1-6 hours.

40. The method for producing glass ceramics according to claim 37, wherein the crystallization process comprises the steps of: the nucleation process is carried out at a 1 st temperature, followed by the crystal growth process at a 2 nd temperature, the 1 st temperature being 470 to 600 ℃, the holding time at the 1 st temperature being 0 to 24 hours, preferably 2 to 15 hours, the 2 nd temperature being 600 to 750 ℃, the holding time at the 2 nd temperature being 0 to 10 hours, preferably 0.5 to 6 hours.

41. The method for producing glass ceramics according to claim 37, wherein the crystallization process comprises the steps of: the nucleation process is performed at a1 st temperature, and then the crystal growth process is performed at a2 nd temperature and a3 rd temperature, wherein the 1 st temperature is 470 to 550 ℃, the holding time at the 1 st temperature is 0 to 24 hours, preferably 2 to 15 hours, the 2 nd temperature is 570 to 630 ℃, the holding time at the 2 nd temperature is 0 to 10 hours, preferably 0.5 to 6 hours, the 3 rd temperature is 650 to 750 ℃, and the holding time at the 3 rd temperature is 0 to 10 hours, preferably 0.5 to 6 hours.